JP2017534699A - Polymer composition - Google Patents

Abstract

Provided are polymer compositions comprising at least two polyethylene polymers, such as regenerated polymer compositions, methods for their production, use of functional fillers in the compositions, and articles formed from the polymer compositions. . A pipe having at least one wall having a nominal inner diameter of at least about 400 mm and an SN of at least about 4, wherein at least one wall is at least about 25 mass based on the total mass of the at least one wall Pipe containing% recycled polymer. [Selection figure] None

Description

  The present invention relates to a polymer composition comprising at least two polyethylene polymers, for example a regenerated polymer composition, a process for its production, the use of functional fillers in the composition, and articles formed from this polymer composition. The present invention relates to a pipe having at least one wall, the pipe having a nominal inner diameter of at least 400 mm and an SN of at least about 4, wherein the at least one wall comprises at least about 25% by weight recycled polymer. And, further, formulated polymer resin compositions suitable for use in such pipes.

It is known to incorporate inorganic particulate fillers such as ground inorganic minerals into polymer compositions for various purposes. Many approaches have been proposed to improve the compatibility between inorganic fillers and polymer compositions. For example, US-A-7732514 describes a composition containing a plastic material, an inorganic particulate solid such as aluminum hydrate and a coupling surface modifier. In the coupling surface modifier, this modifier interacts with both the particulate filler surface and the polymer matrix surface.
In recent years, regeneration of polymer waste materials has been attracting attention. However, the regeneration of polymer waste materials presents a number of problems that are not necessarily encountered during the production of polymer compositions derived from virgin polymers.
As the need for recycling polymer waste materials increases, there is an increasing trend towards the development of new economically feasible methods and compositions for processing polymer waste materials to obtain high quality polymer compositions and articles. There is an increasing demand.

High density polyethylene (HDPE) and polypropylene PP are used in the manufacture of pipes, for example corrugated pipes for use in applications such as drainage and sewage. Because of the limited availability in the market for high purity recycled polypropylene, unused polypropylene is usually used to produce PP pipes.
In general, as the diameter of a pipe made from a polymer increases, the stiffness (ie, load deformation) of the pipe tends to decrease. This can be exacerbated when regenerated and / or filled polymers are used. The stiffness of the pipe can be characterized in terms of stiffness number (SN) according to EN ISO 9969. SN ranges from 1 to 16, with 16 being the hardest. Unused PP is preferred when producing large diameter pipes, for example, pipes having a nominal inner diameter of at least about 400 mm, because large diameter pipes made from unused polypropylene have good mechanical properties ( For example, it is known to show a higher SN). However, unused polypropylene is costly and it is becoming increasingly environmentally desirable to use recycled polymers.

According to a first aspect, the present invention is directed to a polymer composition, the polymer composition comprising:
At least two polyethylene polymers;
A functional filler containing inorganic particles and a surface treatment agent on the surface of the inorganic particles,
At least two polyethylene polymers are bound together;
The first of the at least two polyethylene polymers includes HDPE.
According to a second aspect, the present invention is directed to a masterbatch from which the polymer composition according to the first aspect can be formed.
According to a third aspect, the present invention is directed to a method of manufacturing a product, the method comprising forming the product from a polymer composition according to the first aspect.
According to a fourth aspect, the present invention is directed to a method for reducing the incorporation of polymer components during the manufacture of a product, the method comprising (i) at least two types of HDPE and a surface treating agent on the surface. Providing a preformed polymer composition comprising a functional filler comprising inorganic particulates, and (ii) forming a product therefrom.

According to a fifth aspect, the present invention is directed to a method for reducing the blending of polymer components in a plant for the manufacture of a product, the method comprising: (i) at least two types of HDPE in the plant; Providing a preformed polymer composition comprising a functional filler comprising inorganic particulates having a surface treating agent on the surface; and (ii) forming a product therefrom in a plant.
According to a sixth aspect, the present invention is directed to a method of producing at least two different types of products from the same starting material, the method comprising: (i) at least two types of HDPE; Providing a starting material which is a polymer composition comprising a filler comprising inorganic particulates having a coating on; (ii) forming a first type of product from the starting material; and (iii) at least a second Forming a product of the type from the starting material.

According to a seventh aspect, the present invention is directed to a product formed from the polymer composition according to the first aspect.
According to an eighth aspect, the present invention provides the use of a functional filler comprising inorganic particulates and a surface treatment agent on the surface of the inorganic particulates in a polymer composition comprising at least two polyethylene polymers. For purposes, at least two polyethylene polymers are bonded to the functional filler, and the first of the at least two polyethylene polymers comprises HDPE.
According to a ninth aspect, the present invention is directed to the use of the polymer composition according to the first aspect to improve the mechanical properties of the product formed therefrom.
According to a tenth aspect, the present invention is directed to a method for increasing the diameter of a pipe while maintaining or improving the rigidity of the pipe, the method forming a pipe from a polymer composition according to the first aspect. Including that.

According to an eleventh aspect, the present invention is directed to a method for producing a polymer composition according to the first aspect, comprising combining at least two polyethylene polymers with a functional filler.
According to a twelfth aspect, the present invention is a pipe having at least one wall having a nominal inner diameter of at least about 400 mm and an SN of at least about 4, wherein the at least one wall comprises at least one wall The pipe is intended to contain at least about 25% by weight recycled polymer, based on the total weight of the wall.
According to a thirteenth aspect, the present invention provides a pipe having at least about 400 mm nominal inner diameter and at least about 4 SN at least partially, optionally entirely, of unused polymer, such as unused polypropylene. Is intended for the use of regenerated polymers as bound and as defined by the twelfth aspect.

  According to a fourteenth aspect, the present invention provides an unbound recycled polymer, such as a post-consumer polymer waste (in a pipe having a nominal inner diameter of at least about 400 mm and an SN of at least about 4). Use of a regenerated polymer as bound and as defined by the twelfth aspect to at least partially, optionally entirely replace, unbound regenerated HDPE polymer from, for example, blow molded bottles).

2 is a graph summarizing the toughness / resilience of test pieces prepared according to examples. It is the graph which put together the rigidity / bending elastic modulus of the test piece prepared according to the Example. It is the graph which summarized the breaking elongation of the test piece prepared according to the Example.

Polymer composition comprising at least two polyethylene polymers As stated above, the present invention is a functional filler comprising at least two polyethylene polymers, inorganic particulates and a surface treating agent on the surface of the inorganic particulates. And a polymer composition comprising: At least two polyethylene polymers are combined and the first of the at least two polyethylene polymers includes HDPE (high density polyethylene). Although not wishing to be bound by theory, at least two polyethylene polymers are bound to inorganic particulates via a surface treatment that functions as a coupling modifier, as described below. Conceivable. The terms “first” and “second” used in connection with at least two polyethylene polymers are only used to distinguish between each of the at least two polyethylene polymers.
In general, HDPE is understood to be primarily linear or branched polyethylene polymers having a relatively high crystallinity and melting point and a density of about 0.96 g / cm ³ or greater. Generally, LDPE (low density polyethylene) is relatively low crystallinity and melting point, and about having a density of 0.91 g / cm ³ ~ about 0.94 g / cm ^3, If it is a highly branched polyethylene Understood. In general, LLDPE (Linear Low Density Polyethylene) is understood to be a polyethylene having a significant number of short chain branches and is usually produced by copolymerization of ethylene with long chain olefins. LLDPE is structurally different from conventional LDPE due to the absence of long chain branching.

In certain embodiments, the polyethylene polymer is a regenerated polymer. In certain embodiments, at least a first of the polyethylene polymers is a regenerated polymer. In certain embodiments, recycled polyethylene polymer is a polymer waste, such as post-consumer polymer waste, post-industrial polymer waste, and / or post-agricultural polymer waste. Derived from. In certain embodiments, the polyethylene polymer is recycled post-consumer polymer waste.
At least a first of the polyethylene polymers includes HDPE. In certain embodiments, the first of the polyethylene polymers is at least about 80% by weight HDPE, such as at least about 85% HDPE, or at least about 90%, based on the total weight of the first polyethylene polymer. Or at least about 95% HDPE. In certain embodiments, the first polyethylene polymer consists or consists essentially of HDPE. In certain embodiments, the polyethylene polymer comprises less than 1% by weight of species other than HDPE, eg, less than about 0.5% by weight of species other than HDPE. In certain embodiments, the first polyethylene polymer comprises less than about 10% by weight polypropylene, such as less than about 5% by weight polypropylene, or less than about 1% by weight polypropylene.

  In certain embodiments, the first of the at least two polyethylene polymers has an MFR (melt flow rate) at 190 ° C./2.16 kg of less than 0.75 g / 10 minutes, eg, about 0.72 g / 10. Have an MFR of less than or equal to about 0.70 g / 10 minutes. In certain embodiments, the first of the at least two polyethylene polymers is about 0.10 to about 0.74 g / 10 min, such as about 0.20 to about 0.70 g / 10 min. Or about 0.30 to about 0.60 g / 10 minutes, or about 0.40 to about 0.50 g / 10 minutes, or about 0.50 to about 0.74 g / 10 minutes, or about 0.50. Having an MFR at 190 ° C./2.16 kg of about 0.70 g / 10 min, or about 0.60 to about 0.74 g / 10 min, or about 0.60 to about 0.70 g / 10 min. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of at least less than about 0.02 g / 10 minutes. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.30 to about 0.50 g / 10 min. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.35 to about 0.45 g / 10 min.

The MFR may be determined according to ISO 1133.
In certain embodiments, the first polyethylene polymer is derived from blow molded polyethylene, i.e., the HDPE is a blow molded HDPE, such as that contained in or consisting of a polyethylene bottle. Thus, in certain embodiments, the HDPE of the first polyethylene polymer is recycled blow molded polyethylene.

  In certain embodiments, the second of the at least two polyethylene polymers comprises HDPE. The HDPE of the second polyethylene polymer is different from the HDPE of the first polyethylene polymer, for example, it may have a shorter chain length and / or a lower viscosity than the HDPE of the first polyethylene polymer. In certain embodiments, the second of the polyethylene polymers is at least about 50% by weight HDPE, such as at least about 60% HDPE, or at least about 70%, based on the total weight of the second polyethylene polymer. Of HDPE, or at least about 80% HDPE, or at least about 85% HDPE. In certain embodiments, the second polyethylene polymer comprises less than about 90% HDPE. In certain embodiments, the second polyethylene polymer comprises about 10% or more polypropylene by weight, such as about 10% to about 30% polypropylene, or about 10% to about 20% polypropylene.

  In certain embodiments, the second of the at least two polyethylene polymers has an MFR of 0.75 g / 10 min or greater, eg, at least about 0.77 g / 10 min, or at least 0.80 g / 10 min. Having an MFR at 190 ° C./2.16 kg. In certain embodiments, the second of the at least two polyethylene polymers is about 0.75 to about 15 g / 10 minutes, such as about 0.80 to about 10 g / 10 minutes, or about 0.90. 190 ° C. to about 8 g / 10 min, or about 0.90 to about 6 g / 10 min, or about 1.0 to about 4 g / 10 min, or about 1.0 to about 2.0 g / 10 min. / Has an MFR at 2.16 kg. In certain embodiments, at least a second of the polyethylene polymers has an MFR at 190 ° C./2.16 kg of no more than about 20 g / 10 minutes. In certain embodiments, the second of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 1.0 to about 2.0 g / 10 minutes. In certain embodiments, the second of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 1.25 to about 1.75 g / 10 min.

In certain embodiments, the second polyethylene polymer is derived from injection molded polyethylene, i.e., the HDPE is injection molded HDPE. Thus, in certain embodiments, the HDPE of the second polyethylene polymer is regenerated injection molded polyethylene.
In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.30 to about 0.50 g / 10 min and at least two polyethylene polymers The second of the polymers has an MFR at 190 ° C./2.16 kg of about 1.0 to about 2.0 g / 10 min.

In certain embodiments, the total amount of HDPE present in the polymer composition is from about 50% to about 90% by weight of the polymer composition, such as from about 55% to about 85% by weight of the polymer composition, or About 60% to about 85%, or about 65% to about 85%, or about 70% to about 85%, or about 70% to about 80%, or about 75% to about 80% by mass.
In certain embodiments, the weight ratio of the first polyethylene polymer HDPE to the second polyethylene polymer HDPE is from about 0.5: 1 to about 3: 1, for example from about 1: 1 to about 3: 1. Or about 1: 1 to about 2: 1, or about 1: 1 to about 3: 2.

  In certain embodiments, the polymer composition is about 10% to about 75% by weight of the first polyethylene polymer HDPE, eg, about 20% to about 65% by weight, based on the total weight of the polymer composition. % Or about 30% to about 65% by weight of the first polyethylene polymer HDPE and about 20% to about 45% of the second polyethylene polymer HDPE. In certain embodiments, the polymer composition comprises from about 35% to about 55% by weight of the first polyethylene polymer HDPE and from about 25% to about 40% by weight of the first polymer HDPE. In certain embodiments, the polymer composition comprises about 40% to about 50% by weight of a first polyethylene polymer HDPE and about 25% to about 35% by weight of a second polyethylene polymer HDPE. . In certain embodiments, the polymer composition comprises about 42% to about 47% by weight of a first polyethylene polymer HDPE and about 28% to about 34% by weight of a second polyethylene polymer HDPE. .

In certain embodiments, the relative amount of HDPE is subject to the condition that the total amount of HDPE in the polymer composition is from about 50% to about 90% by weight of the polymer composition.
The polymer composition may comprise at least two polymers other than polyethylene polymers. The polymer composition may comprise an unbound polyethylene polymer.
In certain embodiments, the polymer composition comprises up to about 20% of polymers other than HDPE, such as LDPE, LLDPE and polypropylene, etc., any or all of which are polymer wastes, such as post-consumption polymers. It may be reused from waste. In certain embodiments, the polymer composition is up to about 20%, for example from about 1% to about 20%, or from about 5% to about 18%, based on the total weight of the polymer composition. % By weight, or from about 10% to about 15% by weight, or from about 12 to about 14% by weight polypropylene. In certain embodiments, at least a portion of the polypropylene is derived from the second polyethylene polymer and may be derived from the first polyethylene polymer.
In certain embodiments, the polymer composition may include virgin polymer.

The functional filler may be present in the polymer composition in an amount ranging from about 1% up to about 70% by weight, based on the total weight of the polymer composition. For example, this can be from about 2% to about 60%, or from about 3% to about 50%, or from about 4% to about 40%, or from about 5%, based on the total weight of the polymer composition. % To about 30%, or about 6% to about 25%, or about 7% to about 20%, or about 8% to about 15%, or about 8% to about 12%. %. The functional filler is about 80% or less, such as about 70% or less, or about 60% or less, or about 50% or less, by weight of the polymer composition, based on the total weight of the polymer composition. Or about 40% or less, or about 30% or less, or about 20% or less, or about 50% or less.
The functional filler surface treatment (ie, coupling modifier), preferably the compound of formula (1) as described below, is about 0.01 mass based on the total mass of the polymer composition. % To about 4% by weight, for example, from about 0.02% to about 3.5%, or from about 0.05% to about 1.4% by weight, based on the total weight of the polymer composition Or about 0.1% to about 0.7%, or about 0.15% to about 0.7%, or about 0.3% to about 0.7%, or About 0.5% to about 0.7%, or about 0.02% to about 0.5%, or about 0.05% to about 0.5%, or about 0% 0.1% to about 0.5%, or about 0.15% to about 0.5%, or about 0.2% to about 0.5% by weight. Or in an amount of from about 0.3% to about 0.5% by weight, may be present in the polymer composition.

Polymer compositions and / or articles made therefrom include, for example, resilience (also referred to as toughness), elongation at break, flexural modulus (also referred to as stiffness), and deflection (also referred to as ductility). It can be characterized by advantageous mechanical properties.
In certain embodiments, the polymer composition is
(I) resilience at −20 ° C. greater than 60 kJ / m ² , eg resilience at −20 ° C. of 70 kJ / m ² ; and / or (ii) greater than 32%, eg greater than 65% breaking elongation; and / or (Iii) a flexural modulus greater than 800 MPa, such as greater than 900 MPa, or greater than 980 MPa; and / or (iv) a total deflection at −20 ° C. of at least about 10.0 mm, such as at least about 15.0 mm.

In certain embodiments, the polymer composition, and / or the article made therefrom, is about 80 kJ / m ² to about 400 kJ / m ² , such as about 100 kJ / m ² to about 300 kJ / m ² , or About 100 kJ / m ² to about 200 kJ / m ² , or about 110 kJ / m ² to about 180 kJ / m ² , or about 110 kJ / m ² to about 170 kJ / m ² , or about 120 kJ / m ² to about 160 kJ / M ² , or about 130 kJ / m ² to about 150 kJ / m ² , or about 130 kJ / m ² to about 140 kJ / m ² , or about 140 kJ / m ² to about 170 kJ / m ² , or about 150 kJ. Resilience at −20 ° C. of from / m ² to about 160 kJ / m ² . Resilience / toughness at −20 ° C. can be determined according to ISO179.

In certain embodiments, the polymer composition and / or article made therefrom is about 40% to about 500%, such as about 60% to about 400%, or about 80% to about 300%. Or about 80% to about 200%, or about 80% to about 150%, or about 80% to about 125%, or about 90% to about 120%, or about 90% to about 115%. Or about 90% to about 110%, or about 95% to about 110%, or about 100% to about 105%. The elongation at break can be determined according to IOS 178.
In certain embodiments, the polymer composition, and / or the article made therefrom, is about 900 MPa to about 2000 MPa, such as about 900 to about 1750 MPa, or about 900 to about 1500 MPa, or about 950 to about It has a flexural modulus of 1250 MPa, or about 950 MPa to about 1200 MPa, or about 950 MPa to about 1150 MPa, or about 950 MPa to about 1100 MPa, or about 1000 MPa to about 1100 MPa, or about 1025 MPa to about 1075 MPa. The flexural modulus / stiffness can be determined according to ISO 178.

In certain embodiments, the polymer composition, and / or the article made therefrom, is about 10.0 mm to about 30.0 mm, such as about 12.0 mm to about 30.0 mm, or about 15.0 mm. Have a total deflection at -20 ° C of from about 30.0 mm, or from about 17.5 mm to about 27.5 mm, or from about 20.0 mm to about 25.0 mm.
Thus, the polymer composition may be used to modify, for example, improve or improve the mechanical properties of the product by manufacturing the product from the polymer composition. The mechanical properties may be selected from one or more of resilience (toughness), elongation at break, flexural modulus (stiffness), and deflection (ductility). In this regard, synergistic improvements in mechanical properties such as resilience and deflection are obtained by combining at least two different polyethylene polymers while at the same time maintaining other mechanical properties such as stiffness. Unexpectedly found that it can. Further evidence of this surprising synergy is provided in the following embodiments. The synergistic effect obtained by combining at least different types of polyethylene polymers allows the use of recycled polymer waste and is comparable to polymer compositions that are not combined with different types of polyethylene or unused polymers. In addition, even better mechanical properties can be achieved (along with environmental conservation advantages). Moreover, the coupling effect allows a smaller amount of polymer (recycled or unused) (ie by replacing some with functional fillers) can be used without adversely affecting the mechanical properties. And in some embodiments, improves mechanical properties (along with cost benefits).

In certain embodiments, the polymer composition comprises from about 0.90 g / cm ³ greater than about 1.15 g / cm ³ or less, for example, from about 1.10 g / cm ³ or less of greater than about 1.00 g / cm ³ Density, for example, greater than about 1.00 g / cm ^{3 and} less than about 1.05 g / cm ³ , or about 1.00 to about 1.04 g / cm ³ , or about 1.00 to about 1.03 g / a of cm ^3, or from about 1.00 to about 1.02 g / cm ^3, or a density of about 1.01 g / cm ^3. In certain embodiments, the polymer composition has a density greater than about 1.00 and not greater than about 1.05 g / cm ³ . The density can be determined according to ISO 1183.

  The polymer composition can be characterized by thermal analysis, for example by differential scanning calorimetry (DSC). In certain embodiments, the DSC thermogram of the polymer composition is different from the DSC thermogram of a comparable composition comprising at least two polyethylene polymers that are not both bonded.

Products The articles that can be formed from the polymer composition are numerous and varied. Products include, for example, industrial, commercial, and residential pipes and tubes, such as groundwater and sewage pipes, surface water pipes, cable protection pipes, waterworks pipes, and buildings such as樋, pallets for commercial or residential buildings (including, for example, those used to cover or bridge entire surface defects on roads or walkways, or pallets used in product storage and transport) Including garden deck materials, roads, sidewalks, paved roads, boardwalks and bridge surfaces, or parts thereof.
In one embodiment, the polymer composition is suitable for industrial use, such as use as a pipe. Thus, in certain embodiments, the product is a pipe.

  Unexpectedly, it has been found that the polymer compositions described herein can be used to produce pipes having advantageous mechanical properties. For example, as the diameter of a pipe made from filled polymer increases, the stiffness (ie, load deformation) of the pipe tends to decrease. The stiffness of the pipe can be characterized in relation to the stiffness number (SN) according to EN ISO 9969. SN ranges from 1 to 16, with 16 being the hardest. Based on this, it may be necessary to add an additional polymer composition to compensate for the reduction in stiffness and / or use a smaller amount of filler, since this is usually more expensive than fillers. And increase costs. Surprisingly, it has been found that pipes made from polymer compositions according to the embodiments described herein exhibit high stiffness even at relatively large calibers. For example, it is possible to produce a double wall corrugated pipe having a diameter greater than 400 mm from a composition that is a 100% polymer composition according to embodiments described herein having an SN of 8.

  In certain embodiments, the pipe is a corrugated pipe. In certain embodiments, the pipe is double walled, for example a double wall corrugated pipe. In certain embodiments, the pipe is single walled, such as a single wall corrugated pipe. In embodiments where the pipe is double walled, at least one of the walls may be formed from a polymer composition according to embodiments described herein. In certain embodiments, both walls of a double wall pipe may be formed from a polymer composition according to embodiments described herein.

  In certain embodiments, the pipe is up to about 1000 mm, such as up to about 800 mm, or up to about 700 mm, or up to about 600 mm, or up to about 500 mm, or up to about 400 mm, or up to about 300 mm. Or a nominal inner diameter of up to about 200 mm. In certain embodiments, the pipe has a caliber of at least about 400 mm, or greater than about 400 mm, such as greater than about 400 mm and up to about 700 mm, such as up to about 650 mm, or up to about 600, or up to It has a caliber of less than about 600 mm. Such pipes may be single walled or double walled.

  In certain embodiments, the product may be a road (automobile road, highway, tumor main road, B road, C road, main road, residential road, etc.), sidewalk, paved road, promenade or bridge surface (eg, for vehicles) Bridge surface of a bridge or footbridge). Such an article may be pre-assembled. In certain embodiments, the product is a road, a sidewalk, a paved road, a part of a promenade or bridge surface, or one that is incorporated therein, such as a three-dimensional intersection, a plane intersection, a pavement surface indentation repair piece, or a livestock fence. It is. In certain embodiments, such articles have a hollow core that can accommodate, for example, cables, pipes, and rainwater. In certain embodiments, the surface, such as the top surface, of such an article is roughened to increase friction between the surface and a user (eg, a vehicle or object), thereby reducing slippage. Or eliminate. Roughening is, for example, by shaping or extruding an article such that the surface has regular or irregular ridges, or by embedding certain materials, such as crushed stone, sand, etc. May be performed during the manufacture of the article.

Further, in certain embodiments, the same starting polymer composition is produced from mixed polyolefin raw materials at least two different types of products, at least in part due to the advantageous mechanical properties provided by the polymer composition. Efficiency in the manufacturing process can be obtained. This may be due in part to the synergistic improvement in coupling effects and mechanical properties of at least two polyethylene polymers discussed above. This coupling effect can extend to other polymer types present in the polymer composition, for example, other polyethylene polymers such as polypropylene and LDPE and LLDPE. In this way, the coupling effect generally improves the compatibility of different polymer types and allows for the polymer article from a mixed and regenerated polymer stream with acceptable or even improved mechanical properties. Enable manufacturing. Accordingly, in certain embodiments, a method is provided for producing at least two different types of products from the same starting material, the method comprising: (i) at least two types of HDPE and inorganic particulates. Providing a starting material that is a polymer composition comprising a filler having a coating on the surface of the inorganic particulates; (ii) forming a first type of product from the starting material; (iii) ) Forming at least a second type of product from the starting material.
In certain embodiments, the first and second types of articles are pipes having different calibers, or may be the inner and outer walls of a double wall pipe.
The flexibility of a pipe made from a polymer composition according to certain embodiments described herein is compared to a pipe made from a comparable polymer composition in which both polyethylene polymers are not bonded. , Less increase as temperature rises. This is advantageous when the pipe is placed in a very hot condition, for example at ambient atmospheric temperatures above about 30 ° C.

Functional filler In certain embodiments, the functional filler comprises inorganic particulates and a first compound comprising a terminal propanoic acid group or an ethylene group having one or two adjacent carbonyl groups. Including. The surface treatment agent may be coated on the surface of the inorganic particulate matter. The purpose of the surface treatment agent (eg, coating) is to improve the compatibility of the inorganic particulate filler and the polymer matrix mixed therewith and / or to improve the compatibility of two or more different polymers in the regenerated polymer composition. The improvement is to crosslink or graft these different polymers together. In regenerated polymer compositions containing reclaimed and virgin polymers, the functional filler coating can serve to crosslink or graft different polymers.
In other aspects and embodiments of the invention, the coating further comprises a second compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts, such as stearic acid or calcium stearate.

Inorganic particulate materials For example, inorganic particulate materials are alkaline earth metal carbonates or sulfates such as calcium carbonate, magnesium carbonate, dolomite, gypsum, hydrous kandite clays such as kaolin, halloysite or ball clay, anhydrous (calcined) It may be a kandite clay such as metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or combinations thereof.

A preferred inorganic particulate material for use in the method according to the first aspect of the invention is calcium carbonate. In the following, the present invention will be discussed primarily in the context of calcium carbonate and in the context of the manner in which the calcium carbonate is processed and / or processed. The present invention should not be construed as limited to such embodiments.
The granular calcium carbonate used in the present invention can be obtained from natural sources by grinding. Typically, ground calcium carbonate (GCC) is obtained by crushing and then grinding a mineral source such as chalk, marble or limestone, which is a particle size classification to obtain a product with the desired fineness. Can follow the stages. Other techniques such as bleaching, flotation, and magnetic separation can be used to obtain a product with the desired fineness and / or color. The particulate solid material is pulverized spontaneously, i.e. by grinding between the particles of the solid material itself, or the particulate solid material contains particles of a material different from the calcium carbonate to be ground. It is also possible to grind in the presence of a medium. These processes can be performed in the presence or absence of dispersants and biocides that can be added at any stage of the process.

  Precipitated calcium carbonate (PCC) can be used as a source of granular calcium carbonate in the present invention, and can also be produced by any of the known methods available in the art. TAPPI Monograph Series (TAPPI Monograph Series) No. 30, “Paper Coating Pigments”, pp. 34-35 is suitable for use in preparing products for use in the paper industry, but three main commercial methods for producing precipitated calcium carbonate that can also be used in the practice of the present invention. Describes the method. In all three methods, a calcium carbonate feed, such as limestone, is first calcined to quick lime, which is then hydrated in water to calcium hydroxide or lime milk. In the first method, lime milk is directly carbonated with carbon dioxide gas. This process has the advantage of not producing any by-products and is relatively easy to adjust the properties and purity of the calcium carbonate product. In the second process, lime milk is brought into contact with soda ash to produce a calcium carbonate precipitate and a sodium hydroxide solution by metathesis. The sodium hydroxide can be completely separated from calcium carbonate when the process is used commercially. In the third major commercial process, lime milk is first contacted with ammonium chloride to obtain a calcium chloride solution and ammonia gas. The calcium chloride solution is then contacted with soda ash to produce precipitated calcium carbonate and sodium chloride solution by metathesis. Crystals can be produced as having a wide variety of different shapes and sizes, depending on the particular reaction process used. The three main forms of PCC crystals are the meteorite, rhombohedron, and rhombohedral shapes, all of which are suitable for use in the present invention, including mixtures thereof.

Wet milling of calcium carbonate involves the formation of an aqueous suspension of calcium carbonate, which may then be milled in the presence of a suitable dispersing aid. For more information on wet grinding of calcium carbonate, reference may be made, for example, to EP-A-614948, the entire contents of which are incorporated herein by reference. Inorganic particulates such as calcium carbonate may also be prepared by any suitable dry milling technique.
In some situations, addition of other inorganic materials may be included, for example, one or more kaolins, calcined kaolins, wollastonite, bauxite, talc, titanium dioxide or mica may be present.

  If the inorganic particulate material is obtained from a naturally occurring source, some inorganic impurities may contaminate the ground material. For example, naturally occurring calcium carbonate may exist in a state combined with other minerals. Thus, in some embodiments, the inorganic particulate material includes an amount of impurities. In general, however, the inorganic particulate material used in the present invention will contain less than about 5% by weight of other inorganic impurities, preferably less than about 1% by weight.

Unless stated otherwise, the particle size characteristics referred to herein for inorganic particulate materials give (or essentially the same results) well-known conventional methods used in the field of laser light scattering using CILAS 1064 instruments. Measured by other methods). In laser light scattering techniques, the size of particles in powder, suspension and emulsion can be measured using laser beam diffraction based on the application of Mie theory. Such an apparatus has a predetermined e.d., referred to in the art as an "equivalent spherical diameter" (esd). s. This results in a measurement of the cumulative volume percentage of particles having a size smaller than the d value and its plot. This average particle size d ₅₀ is defined as particles having an equivalent particle size smaller than the d ₅₀ value at 50% by volume. s. This is the value of d measured in this way. The term d ₉₀ is the value of the particle size at which 90% by volume of the particles have a particle size less than that value.

The d ₅₀ of the inorganic particulate is less than about 100 μm, such as less than about 80 μm, such as less than about 60 μm, such as less than about 40 μm, such as less than about 20 μm, such as less than about 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as about 6 μm. Less than, for example, less than about 5 μm, such as less than about 4 μm, such as less than about 3 μm, such as less than about 2 μm, such as less than about 1.5 μm, or such as less than about 1 μm. The d ₅₀ of the inorganic particulate may be greater than about 0.5 μm, for example greater than about 0.75 μm, greater than about 1 μm, for example greater than about 1.25 μm, or for example greater than about 1.5 μm. The d ₅₀ of the inorganic particulates is in the range of 0.5-20 μm, such as in the range of about 0.5-10 μm, such as in the range of about 1 to about 5 μm, such as in the range of about 1 to about 3 μm, such as about 1 to about 2 μm. In the range of about 0.5 to about 2 μm, for example in the range of about 0.5 to 1.5 μm, for example in the range of about 0.5 to about 1.4 μm, for example in the range of about 0.5 to about 1.4 μm. A range, such as a range of about 0.5 to about 1.3 μm, such as a range of about 0.5 to about 1.2 μm, such as a range of about 0.5 to about 1.1 μm, such as about 0.5 to about 1. A range of 0 μm, such as a range of about 0.6 to about 1.0 μm, such as a range of about 0.7 to about 1.0 μm, such as a range of about 0.6 to about 0.9 μm, such as about 0.7 to about It may be in the range of 0.9 μm.

The inorganic particulates have a d ₉₀ (also referred to as a top cut) of less than about 150 μm, such as less than about 125 μm, such as less than about 100 μm, such as less than about 75 μm, such as less than about 50 μm, such as less than about 25 μm, such as about 25 μm. It may be less than 20 μm, such as less than about 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as less than about 6 μm, such as less than about 4 μm, such as less than about 3 μm, or such as less than about 2 μm. Advantageously, the value of d ₉₀ may be less than about 25 μm.
The amount of particles smaller than 0.1 μm is typically about 5% or less by volume.

The inorganic particulates can have a particle stepness of about 10 or more. The particle gradient (ie, the gradient of the particle size distribution of the inorganic particulates) is determined by the following formula:
Stepness = 100 × (d ₃₀ / d ₇₀ )
Where d ₃₀ is less than this d ₃₀ value e. s. the particles with d are present in a proportion of 30% by volume e. s. a value of d, also d ₇₀ is smaller e than the d ₇₀ value. s. the particles with d are present in a proportion of 70% by volume. s. The value of d.
The inorganic particulates may have a particle gradient of about 100 or less. The inorganic particulates can have a particle gradient of about 75 or less, or about 50 or less, or about 40 or less, or about 30 or less. The inorganic particulates can have a particle gradient in the range of about 10 to about 50, or in the range of about 10 to about 40.

The inorganic particulates have been treated with a surface treatment agent, i.e., a coupling modifier, whereby the inorganic particulates have a surface treatment on their surface. In certain embodiments, the inorganic particulate is coated with a surface treatment agent.
The polymer composition may contain one or more secondary filler components, if desired. The secondary filler component may not be treated with the surface treatment agent. Such additional components, if present, are suitably selected from known filler components for the polymer composition. For example, inorganic particulates used in the functional filler may be used in combination with one or more other known secondary filler components such as titanium dioxide, carbon black and talc. In certain embodiments, the polymer composition includes talc as a secondary filler component. In certain embodiments, the weight ratio of inorganic particulate to secondary filler component is from about 1: 1 to about 10: 1, such as from about 1: 1 to about 5: 1, or from about 2: 1 to about 4. : 1. In certain embodiments, the inorganic particulate of the functional filler is calcium carbonate, such as ground calcium carbonate, and the secondary filler component is uncoated talc. When a secondary filler component is used, this is in an amount from about 0.1% to about 50% by weight of the polymer composition, for example from about 1% to about 40% by weight of the polymer composition, or about 2% to about 30%, or about 2% to about 25%, or about 2% to about 20%, or about 3% to about 15%, or about 4% % To about 10% by weight.

Surface treatment agent A surface treatment agent comprises a compound comprising terminal propanoic acid groups or ethylene groups having one or two adjacent carbonyl groups (also referred to herein as a coupling modifier). The function of the agent is to bind the polymer species present in the polymer composition, i.e. to bind at least two polyethylene polymers. While not wishing to be bound by theory, the coupling can be physical (eg, steric) and / or chemical (eg, covalent or van der Waals (van) between the polymer and the surface treatment material. der Waals) chemical bonds) and other interactions.

In one embodiment, the surface treatment agent (ie, coupling modifier) has the following formula (1):
A- (X-Y-CO) m (O-B-CO) n OH (1)
Where
A is a moiety containing a terminal ethylenic bond having 1 or 2 adjacent carbonyl groups;
X is O and m is 1-4, or X is N and m is 1.
Y is C _1-18 alkylene or C _2-18 alkenylene;
B is C _2-6 alkylene, n is 0-5,
However, when A contains two carbonyl groups adjacent to the ethylene group, X is N.

In one embodiment, A—X— is a residue of acrylic acid, where (O—B—CO) _n may be a residue of δ-valerolactone or ε-caprolactone or a mixture thereof. , N may be 0.
In another embodiment, AX- is a residue of maleimide, wherein (O—B—CO) _n may be a residue of δ-valerolactone or ε-caprolactone or a mixture thereof, n may be 0.
Specific examples of coupling modifiers are β-carboxyethyl acrylate, β-carboxyhexyl maleimide, 10-carboxydecyl maleimide and 5-carboxypentyl maleimide. Examples of coupling modifiers and methods for their preparation are described in US-A-7732514, the entire contents of which are hereby incorporated by reference.
In another embodiment, the coupling modifier is β-acryloyloxypropanoic acid or an oligomeric acrylic acid represented by the following formula (2):
_{CH 2 = CH-COO [CH} 2 -CH 2 -COO] n H (2)
In formula, n represents the number of the range of 1-6.
In one embodiment, n is 1, or 2, or 3, or 4, or 5, or 6.

The oligomeric acrylic acid of formula (2) is a temperature in the range of about 50 ° C. to 200 ° C. in the presence of 0.001 to 1% by weight of a polymerization inhibitor, which may be under high pressure and in the presence of an inert solvent. Up to, it can be produced by heating acrylic acid. Examples of coupling modifiers and methods for their preparation are described in US-A-4267365, the entire contents of which are incorporated herein by reference.
In another embodiment, the coupling modifier is β-acryloyloxypropanoic acid. This species and its method of manufacture are described in US-A-3888912, the entire contents of which are incorporated herein by reference.

  The surface treatment agent is present in the functional filler in an amount effective to achieve the desired result. This amount will vary from one coupling modifier to another and may depend on the exact composition of the inorganic particulates. For example, the coupling modifier may be present in an amount of about 5% or less, such as about 2% or less, or such as about 1.5% or less, based on the total weight of the functional filler. In one embodiment, the coupling modifier is about 1.2% or less, such as about 1.1% or less, such as about 1.0% or less, such as about 1.0%, based on the total weight of the functional filler. 0.9% by weight or less, for example about 0.8% by weight or less, for example about 0.7% by weight or less, for example about 0.6% by weight or less, for example about 0.5% by weight or less, for example about 0.4% by weight. Below, for example in an amount of about 0.3% by weight or less, for example about 0.2% by weight or less, or for example about 0.1% by weight or less, in the functional filler. Typically, the coupling modifier is present in the functional filler in an amount greater than about 0.05% by weight. In further embodiments, the coupling modifier is in the range of about 0.1 to 2 wt%, such as in the range of about 0.2 to about 1.8 wt%, or about 0.3 to about 1.6 wt%. Or about 0.4 to about 1.4% by weight, or about 0.5 to about 1.3% by weight, or about 0.6 to about 1.2% by weight, or about In the functional filler in an amount in the range of 0.7 to about 1.2 wt%, or in the range of about 0.8 to about 1.2 wt%, or in the range of about 0.8 to about 1.1 wt%. Exists.

In certain embodiments, the terminal propanoic acid group or ethylene group compound / compound (s) having one or two adjacent carbonyl groups is the single species present in the surface treatment agent.
In certain embodiments, the surface treatment agent further comprises a second compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts and combinations thereof.

In one embodiment, the one or more fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidin. Selected from the group consisting of acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid and combinations thereof. In another embodiment, the one or more fatty acids are saturated fatty acids or unsaturated fatty acids. In another embodiment, the fatty acids are C ₁₂ -C ₂₄ fatty acids, such as C ₁₆ -C ₂₂ fatty acids, which may be saturated or unsaturated. In one embodiment, the one or more fatty acids is stearic acid and may be combined with other fatty acids.

  In another embodiment, the salt of one or more fatty acids is a metal salt of the aforementioned fatty acids. The metal may be an alkali metal or alkaline earth metal or zinc. In one embodiment, the second compound is calcium stearate.

When present, the second compound is present in the functional filler in an amount effective to achieve the desired result. This amount will vary from one coupling modifier to another and may depend on the exact composition of the inorganic particulates. For example, the second compound may be present in an amount of about 5% or less, such as about 2% or less, or such as about 1% or less, based on the total weight of the functional filler. In one embodiment, the second compound is about 0.9% or less, such as about 0.8% or less, such as about 0.7% or less, such as about 0, based on the total weight of the functional filler. .6% or less, such as about 0.5% or less, such as about 0.4% or less, such as about 0.3% or less, such as about 0.2% or less, or such as about 0.1%. It is present in the functional filler in the following amounts. Typically, the second compound, when present, is present in the functional filler in an amount greater than about 0.05% by weight. The mass ratio of the coupling modifier to the second compound ranges from about 5: 1 to about 1: 5, such as from about 4: 1 to about 1: 4, such as from about 3: 1 to about 1: 3. In the range of about 2: 1 to about 1: 2, or for example about 1: 1. The amount of coating comprising the first compound (i.e., coupling modifier) and the second compound (i.e., one or more fatty acids or salts thereof) is such that a single layer deposition amount is provided on the surface of the inorganic particulates. Is the amount calculated. In certain embodiments, the mass ratio of the first compound to the second compound ranges from about 4: 1 to about 1: 3, such as from about 4: 1 to about 1: 2, such as from about 4: 1. A range of about 1: 1, such as a range of about 4: 1 to about 2: 1, such as a range of about 3.5: 1 to about 1: 1, such as a range of about 3.5: 1 to 2: 1; Or, for example, in the range of about 3.5: 1 to about 2.5: 1.
In certain embodiments, the surface treatment agent does not include a compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts.

  The polymer composition may further comprise a peroxide-containing additive. In one embodiment, the peroxide-containing additive comprises dicumyl peroxide or 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane. The peroxide-containing additive need not necessarily be included in the surface treatment agent, but can instead be added during the blending operation of the functional filler and the polymer, as will be described below. For example, in some polymer systems such as HDPE, inclusion of peroxide-containing additives can facilitate cross-linking of polymer chains. In other polymer systems such as polypropylene, breakage of the polymer chain can be promoted by including a peroxide-containing additive. The peroxide-containing additive can be present in an amount effective to achieve the desired result. This amount is different for each coupling modifier and may depend on the exact composition of the inorganic particulates and polymer. For example, the peroxide-containing additive is about 1% or less, such as about 0.5% or less, such as 0.1%, based on the weight of polymer in the polymer composition to which the peroxide-containing additive is to be added. %, Such as about 0.09% or less, such as about 0.08% or less, or such as about 0.06% or less. Typically, the peroxide-containing additive, if present, is present in an amount greater than about 0.01% by weight, based on the weight of the polymer.

  The functional filler is preferably combined with inorganic particulates, surface treatments and optional peroxide-containing additives, using conventional methods, for example, using a steel and cowlishaw high strength mixer. It can manufacture by mixing at the temperature of 80 degrees C or less. The surface treating agent compound (s) can be applied after the inorganic particulates have been crushed but before the inorganic particulates are added to any regenerated polymer composition. For example, the surface treatment agent can be added to the inorganic particles in the stage of mechanically deaggregating the inorganic particles. The surface treatment agent can be applied during deagglomeration performed in a milling machine.

Optional additional filler components The functional filler may further comprise an antioxidant. Suitable antioxidants include, but are not limited to, organic molecules consisting of hindered phenols and amine derivatives, organic molecules consisting of phosphates and low molecular weight hindered phenols, and thioesters. Exemplary antioxidants include Irganox 1010 and Irganox 215, and blends of Irganox 1010 and Irganox 215.

Method for Producing Polymer Composition In certain embodiments, the polymer composition is produced by a method comprising combining at least two polyethylene polymers with a functional filler.
The compounding operation itself is a technique well known to those skilled in the art of polymer processing and manufacturing. It is understood in the art that compounding operations are distinct from blending or mixing steps that are performed at a temperature lower than the temperature at which the components become molten.
Such methods include compounding and extrusion processes. The compounding process can be carried out using a twin screw compounder, for example, a Baker Perkins 25 mm twin screw compounder. The polymer, functional filler and optional peroxide-containing additive can be premixed and fed from a single hopper. The resulting melt can be cooled, for example, in a water bath and then pelletized.

  The formulated composition may further comprise additional components such as slip aids (eg, Erucamide), processing aids (eg, Polybatch® AMF-705), mold release agents and antioxidants. An agent can be included. Suitable mold release agents will be readily apparent to those skilled in the art and include fatty acids and the zinc, calcium, magnesium and lithium salts of fatty acids and organophosphates. Specific examples thereof are stearic acid, zinc stearate, calcium stearate, magnesium stearate, lithium stearate, calcium oleate and zinc palmitate. Slip and processing aids, and mold release agents are added in amounts less than about 5% by weight, based on the weight of the masterbatch. The polymeric article, including the articles described above, can then be subjected to an extrusion, compression molding or injection molding process utilizing conventional techniques known in the art, as will be readily apparent to those skilled in the art. it can.

In certain embodiments, the at least two polyethylene polymers are each contained in separate polymer streams and fed separately to the blender. For example, a first polyethylene containing HDPE is fed to the blender as a first polymer stream, a second polyethylene polymer is fed to the blender as a second polymer stream, and the functional filler is a third polymer stream. Supplied as a stream to the blender. In such embodiments, the second polymer stream comprising the second polyethylene polymer may be part of a polymer stream comprising other polymer components such as polypropylene, LDPE, and / or LLDPE. In other embodiments, any other polymer component may be fed to the blender via a separate feed stream.
In certain embodiments, the at least two polyethylene polymers are part of the same polymer stream. Thus, in such an embodiment, a single feed stream that may include at least two polyethylene polymers and other polymer components such as polypropylene, LDPE, and / or LLDPE is fed to the blender.

In certain embodiments, the functional filler is not contacted with the polymer prior to blending with the at least two polyethylene polymers.
The relative amounts of each component will be such that the polymer composition according to the present invention can be prepared.
Conveniently, during manufacture, at least two polyethylene polymers are included in the polymer composition, and in order for the polymer composition to exhibit favorable mechanical properties, the manufacture of articles from the polymer composition (eg, customer's The need to further blend polymer components (in the facility) can be reduced or eliminated, i.e., reduced.
Accordingly, a method is provided for mitigating blending of polymer components during manufacture of a product, the method comprising (i) at least two types of HDPE and inorganic particulates on a surface of the inorganic particulates. Providing a preformed polymer composition comprising a functional filler having a treating agent and (ii) forming a product therefrom.

The product can be any of the products described herein.
The product will typically be manufactured in a plant suitable for manufacturing the article. Accordingly, in certain embodiments, a method is provided for mitigating blending of polymer components in a plant for product manufacture. Thus, a masterbatch containing bound polymer is mixed with additional polymer prior to manufacture of the article using the masterbatch (eg, mixing additional polymer to improve the mechanical properties of the article). There seems to be no need. The ability to use a polymer composition to produce an article without further blending of the ingredients means that this requires little or no additional raw material beyond the polymer composition in order to reduce raw material costs. Energy utilization associated with environmental benefits, which is advantageous and reduces plant costs (because the manufacturer does not need to have on-site blending equipment and requires less energy) Reduce.

For the avoidance of doubt, this application is intended for the purposes described in the following numbered paragraphs:
1. At least two polyethylene polymers;
A functional filler containing inorganic particles and a surface treatment agent on the surface of the inorganic particles,
A polymer composition wherein the first of the at least two polyethylene polymers comprises HDPE.
1A. The polymer composition of paragraph 1 wherein at least two polyethylene polymers are bound.

2. A polymer composition according to paragraph 1 or 1A, wherein the polyethylene polymer is a recycled polymer, eg a polymer waste after recycled consumption.
3. Paragraph 1, 1A or 2 having (i) resilience at −20 ° C. greater than 60 kJ / m ² and / or (ii) elongation at break greater than 32% and / or (iii) flexural modulus greater than 800 MPa The polymer composition described.
4). A second one of the at least two polyethylene polymers includes HDPE, wherein the HDPE of the second polyethylene polymer is different from the HDPE of the first polyethylene polymer in any one of numbered paragraphs 1-3. The polymer composition described.
5. The first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of less than 0.75 g / 10 minutes, and the second of the at least two polyethylene polymers 5. The polymer composition according to any one of numbered paragraphs 1 to 4, which may have an MFR at 190 ° C./2.16 kg of 75 g / 10 min or more.

6). 6. Polymer composition according to any one of the numbered paragraphs 1 to 5, wherein the HDPE of the first polyethylene polymer is a blow molded HDPE, for example a regenerated blow molded HDPE.
7). 7. A polymer composition according to any one of numbered paragraphs 1 to 6, further comprising polypropylene, wherein the polypropylene may be recycled polypropylene.
8). Inorganic particulates are alkaline earth metal carbonates or sulfates such as calcium carbonate, magnesium carbonate, dolomite, gypsum, hydrous kandite clay such as kaolin, halloysite or ball clay, anhydrous (calcined) kandite clay such as metakaolin Or numbered paragraphs 1 to 7, which are fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or combinations thereof Polymer composition.
9. 9. A polymer composition according to paragraph 8, wherein the inorganic particulate comprises or is calcium carbonate, such as ground calcium carbonate.

10. 9. The polymer composition according to paragraph 8, wherein the polymer composition further comprises a second filler that has not been treated with a surface treatment agent, and the second filler may be talc.
11. 11. The polymer composition according to any one of numbered paragraphs 1 to 10, wherein the surface treatment agent comprises a first compound comprising a terminal propanoic acid group having 1 or 2 adjacent carbonyl groups or an ethylene group. .
12 The first compound has the formula (1):
A- (X-Y-CO) m (O-B-CO) n OH (1)
Where
A is a moiety containing a terminal ethylenic bond having 1 or 2 adjacent carbonyl groups;
X is O and m is 1-4, or X is N and m is 1;
Y is C _1-18 alkylene or C _2-18 alkenylene;
B is C _2-6 alkylene, n is 0-5,
However, the polymer composition according to paragraph 11, wherein X is N when A contains two carbonyl groups adjacent to the ethylene group.

13. 13. The polymer composition according to paragraph 11 or 12, wherein the surface treatment agent does not contain a compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts.
14 14. The polymer composition according to any one of numbered paragraphs 1 to 13, wherein the functional filler is present in an amount ranging from about 5 to about 25% by weight of the polymer composition.
15. 15. The polymer composition according to any one of numbered paragraphs 1 to 14, wherein the HDPE of the first polyethylene polymer is present in an amount ranging from about 10 to about 75% by weight of the polymer composition.
16. A masterbatch in which the polymer composition according to any one of numbered paragraphs 1 to 15 can be formed.

17. A method of manufacturing a product, the method comprising forming the product from a polymer composition according to any one of numbered paragraphs 1-15.
18. A method for reducing blending of polymer components during production of a product, comprising: (i) at least two types of HDPE, and a functional filler containing the inorganic particles having a surface treatment agent on the surface of the inorganic particles; Providing a preformed polymer composition comprising: (ii) forming a product therefrom.
19. A method for reducing blending of polymer components in a plant for producing a product, the method comprising: (i) said inorganic having at least two types of HDPE and a surface treatment agent on the surface of inorganic particulates in the plant. Providing a preformed polymer composition comprising a functional filler comprising particulates, and (ii) forming a product therefrom in a plant.

20. A method for producing at least two different types of products from the same starting material, comprising (i) at least two types of HDPE and said inorganic particulates having a coating on the surface of the inorganic particulates Providing a starting material that is a polymer composition comprising: (ii) forming a first type of product from the starting material; and (iii) forming at least a second type of product from the starting material. A method comprising:
21. 21. The method of paragraph 20, wherein the first and second types of articles are pipes having different calibers.
22. A method for improving the mechanical properties of a product comprising forming the product from a polymer composition comprising at least two polyethylene polymers, wherein the at least two polyethylene polymers are bonded to the functional filler. Wherein the first of the at least two polyethylene polymers comprises HDPE.

23. A product formed from the polymer composition according to any one of the numbered paragraphs 1 to 15.
24. 24. A product according to paragraph 23, wherein the article is a pipe.
25. Use of a functional filler comprising inorganic particulates and a surface treating agent on the surface of the inorganic particulates in a polymer composition comprising at least two polyethylene polymers, wherein the at least two polyethylene polymers are functional. Use wherein the first of the at least two polyethylene polymers bound to the filler comprises HDPE.
26. Use of a polymer composition according to any one of the numbered paragraphs 1 to 15 for improving the mechanical properties of a product formed therefrom.
27. A method of increasing the diameter of a pipe while maintaining or improving the stiffness of the pipe, the method comprising forming the pipe from a polymer composition according to any one of numbered paragraphs 1 to 15. Including.

28. 16. A method for producing a polymer composition according to any one of numbered paragraphs 1 to 15, comprising blending at least two polyethylene polymers with a functional filler.
29. 29. The method of paragraph 28, wherein at least two polyethylene polymers are each included in separate polymer streams.
30. 29. The method of paragraph 28, wherein the at least two polyethylene polymers are part of the same polymer stream.
31. 31. A method according to any one of paragraphs 28 to 30, wherein the functional filler is not contacted with the polymer before it is combined with the at least two polyethylene polymers.

A pipe having at least one wall and having a nominal inside diameter of at least about 400 mm and an SN of at least about 4 It has been found that it can be manufactured. More specifically, it has been found that pipes containing regenerated compositions according to embodiments described herein exhibit high stiffness even at relatively large calibers. This makes it possible to reduce the wider use of regenerated polymers and the dependence on unused polymers, providing cost and environmental benefits.

  Accordingly, a pipe having at least one wall is provided, the pipe having a nominal inner diameter of at least about 400 mm and a stiffness number (SN) of at least about 4 as determined according to EN ISO 9969, and at least one The wall includes at least about 25% by weight recycled polymer, based on the total weight of at least one wall. In certain embodiments, at least one wall comprises at least about 30% by weight recycled polymer, such as at least about 35% by weight recycled polymer, or at least about 40% by weight recycled polymer, or at least about 45% by weight. Recycled polymer, or at least about 50% by weight recycled polymer, or at least about 55% by weight recycled polymer, or at least about 60% by weight recycled polymer, or at least about 65% by weight recycled polymer, or at least about 70% by weight. Recycled polymer, or at least about 75% by weight recycled polymer. In certain embodiments, at least one wall has a maximum of about 99% by weight of regenerated polymer, for example, a maximum of about 95% by weight of regenerated polymer, or a maximum of about 90%, based on the total weight of at least one wall. % By weight of recycled polymer, or up to about 85% by weight of recycled polymer, or up to about 80% by weight of recycled polymer, or up to about 75% by weight of recycled polymer.

This pipe may be used for unpressurized underground drainage and sewage applications.
In certain embodiments, the pipe has an SN of at least about 5, or at least about 6, or at least about 7, or at least about 8. In certain embodiments, the pipe has an SN of about 16 or less, or about 14 or less, or about 12 or less, or about 10 or less. In such or certain embodiments, the pipe is at most about 1000 mm, such as at most about 900 mm, or at most about 800 mm, or at most about 700 mm, or at most about 650 mm, or at most And has a nominal inner diameter of about 600 mm. In certain embodiments, the pipe has a nominal inner diameter of at least about 450 mm, or at least about 500 mm, or at least about 550 mm, or at least about 600 mm.
In certain embodiments, the pipe may be single walled or double walled. In certain embodiments, the pipe is a corrugated pipe. In certain embodiments, the pipe is double walled, such as a corrugated double wall pipe. In certain embodiments, the pipe is single-walled, such as a corrugated single-walled pipe. In embodiments where the pipe is double walled, the at least one wall may be an inner wall. In certain embodiments, at least one wall is an outer wall. In certain embodiments, both the inner wall or the outer wall may comprise at least about 25% by weight of the regenerated polymer according to embodiments described herein, and the blended polymer according to embodiments described herein. You may form from a resin composition. In certain embodiments, both walls of a double wall pipe may be formed from a compounded polymer resin composition according to embodiments described herein.

In certain embodiments, the at least one wall is from about 0.5 mm to about 10 mm, such as from about 1 mm to about 8 mm, or from about 2 mm to about 6 mm, or from about 2 mm to about 5 mm, or from about 2 mm. It has a wall thickness of about 4 mm, or about 3 mm to about 4 mm. In certain embodiments, the inner and outer walls of the double-walled pipe are each separately about 0.5 mm to about 10 mm, such as about 1 mm to about 8 mm, or about 2 mm to about 6 mm, or about 2 mm. Have a wall thickness of about 5 mm, or about 2 mm to about 4 mm, or about 3 mm to about 4 mm. In such embodiments, the inner and outer walls may be the same or different wall thickness.
In certain embodiments, the pipe meets the requirements of the standard BS EN 13476-3: 2007 + A1: 2009 as long as the standard is for unpressurized underground drainage and sewage pipes.

In addition to SN, this pipe can be determined by measuring other advantageous mechanical properties, such as impact strength (Unshaped Charpy impact strength at -20 ° C. according to ISO 179, Can be characterized in terms of resilience) and elongation at break (as can be determined according to ISO 178).
In certain embodiments, at least one wall of the pipe has the following:
(V) an impact strength greater than 70 kJ / m ^{2 at} −20 ° C .; and / or (vi) an elongation at break greater than 10.

In certain embodiments, at least one wall of the pipe has the following:
(I) an impact strength at −20 ° C. greater than 120 kJ / m ² ; and / or (ii) an elongation at break greater than 60.
Thus, the mechanical properties of at least one wall of the pipe may be further improved by the incorporation of impact modifiers. Impact modifiers are additives that improve the impact strength and elongation at break of single or double walled pipes having a nominal inner diameter of at least about 400 mm.
Thus, in certain embodiments, at least one wall includes an impact modifier, such as up to about 20% by weight impact modifier, based on the total weight of the regenerated polymer and functional filler, For example, from about 0.1 wt% to about 20 wt%, or from about 0.5 wt% to about 15 wt%, or from about 1 wt%, based on the total weight of the regenerated polymer and any functional filler About 12.5%, or about 2% to about 12%, or about 1% to about 10%, or about 1% to about 8%, or about 1% to About 6% by weight, or about 1% to about 4% by weight of impact modifier.

In certain embodiments, the impact modifier is an elastomer, such as a polyolefin elastomer. In certain embodiments, the polyolefin elastomer is a copolymer of ethylene and another olefin (eg, alpha-olefin), such as octane, and / or butene and / or styrene. In certain embodiments, the impact modifier is a copolymer of ethylene and octene. In certain embodiments, the impact modifier is a copolymer of ethylene and butene.
In certain embodiments, the impact modifier, eg, a polyolefin copolymer as described above, such as an ethylene-octene copolymer, has a density of about 0.80 to about 0.95 g / cm ³ and / or about 0.1. Melt flow rate (MFR) from 2 g / 10 min (2.16 kg at 190 ° C.) to about 30 g / 10 min (2.16 kg at 190 ° C.), for example, about 0.5 g / 10 min (at 190 ° C. 2.16 kg) to about 20 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 15 g / 10 min (2 at 190 ° C. .16 kg), or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 10 g / 10 min (2.16 kg at 190 ° C.), or about 0.5 g / 10 min (190 ° C. 2.16 kg) to about 7.5 g / 1 Minutes (2.16 kg at 190 ° C.), or about 0.5 g / 10 minutes (2.16 kg at 190 ° C.) to about 5 g / 10 minutes (2.16 kg at 190 ° C.), or about 0. 5 g / 10 min (2.16 kg at 190 ° C.) to about 4 g / 10 min (2.16 kg at 190 ° C.) or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 3 g / 10 minutes (2.16 kg at 190 ° C.), or about 0.5 g / 10 minutes (2.16 kg at 190 ° C.) to about 2.5 g / 10 minutes (2.16 kg at 190 ° C.), Or about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 2 g / 10 min (2.16 kg at 190 ° C.) or about 0.5 g / 10 min (2.16 kg at 190 ° C.) ) To about 1.5 g / 10 min (2.16 kg at 190 ° C.). The MFR can be determined according to ISO 1133. In such or certain embodiments, the impact modifier is an ethylene-octene copolymer having a density of about 0.85 to about 0.86 g / cm ³ . An exemplary impact modifier is a polyolefin elastomer manufactured by DOW under the trade name of Engage (RTM), for example Engage (RTM) 8842. In such embodiments, the compounded polymer resin may further comprise an antioxidant, as described herein.

  In certain embodiments, the impact modifier is a styrene and butadiene based copolymer, such as a linear block copolymer based on styrene and butadiene. In such embodiments, the impact modifier is from about 1 to about 5 g / 10 min (200 ° C. at 5 kg), for example from about 2 g / 10 min (200 ° C. at 5 kg) to about 4 g / 10 min. It may have an MFR of (from 200 ° C. at 5 kg) or from about 3 g / 10 min (200 ° C. at 5 kg) to about 4 g / 10 min (200 ° C. at 5 kg). In such embodiments, the compounded polymer resin may further include a peroxide-containing additive, such as di-cumyl peroxide, as described herein.

  In certain embodiments, the impact modifier is a styrene and ethylene / butene based triblock copolymer. In such embodiments, the impact modifier is from about 15 g / 10 min (200 ° C. at 5 kg) to about 25 g / 10 min (200 ° C. at 5 kg), for example, about 20 g / 10 min (5 kg At 200 ° C.) to about 25 g / 10 min (200 ° C. at 5 kg).

In certain embodiments, the at least one wall of the pipe is at least about 100 kJ / m ² , such as at least about 110 kJ / m ² , or at least about 120 kJ / m ² , or at least about 130 kJ / m ² . Or at least about 150 kJ / m ² , or at least about 200 kJ / m ² , or at least about 250 kJ / m ² , or at least about 300 kJ / m ² , or at least about 350 kJ / m ² , or at least about 400 kJ / M ² impact strength. In certain embodiments, at least one wall of the pipe fails to bend 100% with the addition of at least about 2.5% by weight of the impact modifier, based on the total weight of the regenerated polymer and functional filler. do not do.

  In certain embodiments, the at least one wall is about 20% to about 250%, such as about 40% to about 200%, or about 40% to about 175%, or at least about 60%. Or having an elongation at break of at least about 80%, or at least about 100%, or at least about 120%, or at least about 130%, or at least about 140%, or at least about 150%. The elongation at break can be determined according to ISO 178.

  In certain embodiments, the pipe further comprises unused polypropylene. In certain embodiments, the pipe is at least about 5% by weight unused polypropylene, or at least about 10% by weight unused polypropylene, or at least about 20% by weight unused, based on the total weight of the pipe. Of polypropylene. In certain embodiments, the pipe comprises at least about 35% by weight unused polypropylene, or at least about 50% by weight unused polypropylene, or up to about 75% by weight unused polypropylene. In certain embodiments, where the pipe comprises at least about 50% by weight virgin polypropylene, the pipe is a double-walled pipe and the at least one wall comprising at least about 25% by weight recycled polymer is an inner wall or an outer wall. But not both the inner wall or the outer wall. In certain embodiments where the pipe is a single wall pipe, the pipe is less than about 50% by weight unused polypropylene, or less than about 35% by weight unused polypropylene, or less than about 20% by weight unused. Or less than about 10% by weight of unused prepropylene, or less than about 5% by weight of unused prepropylene. In certain embodiments, the pipe does not include unused polypropylene.

In certain embodiments, the pipe comprises HDPE from a source other than that of the regenerated polymer described herein. For example, the pipe may include unbound HDPE. In certain embodiments, the total amount of HDPE in the pipe (from the regenerated polymer described herein or from a source other than that of the regenerated polymer described herein) is Constituting at least about 50% by weight of the pipe, for example at least about 60% by weight of the pipe, or at least about 70% by weight of the pipe, or at least about 80% by weight of the pipe.
In certain embodiments, the recycled polymer is a mixture of different polymer types, such as a mixture of polyethylene (PE) and polypropylene (PP), such as a mixture of HDPE and PP, or HDPE, PP and low density polyethylene ( LDPE), or a mixture of at least two different types of HDPE and PP, such as HDPE from blow molded bottles, HDPE from sources other than blow molded bottles, and PP. including.

  In a specific embodiment, the regenerated polymer includes at least two polyethylene polymers, and may include a functional filler including inorganic particles and a surface treatment agent on the surface of the inorganic particles. At least two polyethylene polymers are conveniently combined and the first of the at least two polyethylene polymers comprises HDPE (high density polyethylene). While not wishing to be bound by theory, at least two polyethylene polymers, when combined, bind to inorganic particulates via a surface treatment that functions as a coupling modifier, as described below. It is thought that. The terms “first” and “second” used in connection with at least two polyethylene polymers are only used to distinguish between each of the at least two polyethylenes.

In general, HDPE is understood to be primarily linear or branched polyethylene polymers having a relatively high crystallinity and melting point and a density of about 0.96 g / cm ³ or greater. Generally, LDPE (low density polyethylene) is relatively low crystallinity and melting point, and about having a density of 0.91 g / cm ³ ~ about 0.94 g / cm ^3, If it is a highly branched polyethylene Understood. In general, LLDPE (Linear Low Density Polyethylene) is understood to be a polyethylene having a significant number of short chain branches and is usually produced by copolymerization of ethylene with long chain olefins. LLDPE is structurally different from conventional LDPE due to the absence of long chain branching.
In certain embodiments, the recycled polymer (s) are derived from post-consumer polymer waste, spent industrial waste, and / or spent agricultural polymer waste. In certain embodiments, at least the polyethylene polymer is recycled post-consumer polymer waste.

  In certain embodiments, at least a first of the polyethylene polymers comprises HDPE. In certain embodiments, the first of the polyethylene polymers is at least about 80% by weight HDPE, such as at least about 85% HDPE, or at least about 90%, based on the total weight of the first polyethylene polymer. Or at least about 95% HDPE. In certain embodiments, the first polyethylene polymer consists or consists essentially of HDPE. In certain embodiments, the polyethylene polymer comprises less than 1% by weight of species other than HDPE, eg, less than about 0.5% by weight of species other than HDPE.

  In certain embodiments, the first of the at least two polyethylene polymers has an MFR (melt flow rate) at 190 ° C./2.16 kg of less than 0.75 g / 10 minutes, eg, 0.72 g / 10 minutes. Having an MFR of 0.70 g / 10 min or less. In certain embodiments, the first of the at least two polyethylene polymers is about 0.10 to about 0.74 g / 10 min, such as about 0.20 to about 0.70 g / 10 min. Or about 0.30 to about 0.60 g / 10 minutes, or about 0.40 to about 0.50 g / 10 minutes, or about 0.50 to about 0.74 g / 10 minutes, or about 0.50. Having an MFR at 190 ° C./2.16 kg of about 0.70 g / 10 min, or about 0.60 to about 0.74 g / 10 min, or about 0.60 to about 0.70 g / 10 min. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of at least less than 0.02 g / 10 minutes. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.30 to about 0.50 g / 10 min. In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.35 to about 0.45 g / 10 min.

In certain embodiments, the first polyethylene polymer is derived from blow molded polyethylene, i.e., the HDPE is a blow molded HDPE, such as that contained in or consisting of a polyethylene bottle. Thus, in certain embodiments, the HDPE of the first polyethylene polymer is recycled blow molded polyethylene.
In certain embodiments, the second of the at least two polyethylene polymers comprises HDPE. The HDPE of the second polyethylene polymer is different from the HDPE of the first polyethylene polymer, for example, it may have a shorter chain length and / or a lower viscosity than the HDPE of the first polyethylene polymer. In certain embodiments, the second of the polyethylene polymers is at least about 50% by weight HDPE, such as at least about 60% HDPE, or at least about 70%, based on the total weight of the second polyethylene polymer. Of HDPE, or at least about 80% HDPE, or at least about 85% HDPE. In certain embodiments, the second polyethylene polymer comprises less than about 90% HDPE.

  In certain embodiments, the second of the at least two polyethylene polymers has an MFR of 0.75 g / 10 min or greater, eg, at least 0.77 g / 10 min, or at least 0.80 g / 10 min. It has an MFR at 190 ° C./2.16 kg. In certain embodiments, the second of the at least two polyethylene polymers is about 0.75 to about 15 g / 10 minutes, such as about 0.80 to about 10 g / 10 minutes, or about 0.90. 190 ° C. to about 8 g / 10 min, or about 0.90 to about 6 g / 10 min, or about 1.0 to about 4 g / 10 min, or about 1.0 to about 2.0 g / 10 min. / Has an MFR at 2.16 kg. In certain embodiments, at least a second of the polyethylene polymers has an MFR at 190 ° C./2.16 kg of no more than about 20 g / 10 minutes. In certain embodiments, the second of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 1.0 to about 2.0 g / 10 minutes. In certain embodiments, the second of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 1.25 to about 1.75 g / 10 min.

In certain embodiments, the second polyethylene polymer is derived from injection molded polyethylene, i.e., the HDPE is injection molded HDPE. Thus, in certain embodiments, the HDPE of the second polyethylene polymer is regenerated injection molded polyethylene.
In certain embodiments, the first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of about 0.30 to about 0.50 g / 10 min and at least two polyethylene polymers The second of the polymers has an MFR at 190 ° C./2.16 kg of about 1.0 to about 2.0 g / 10 min.

In certain embodiments, the total amount of HDPE present in the regenerated polymer is from about 50% to about 90% by weight of the regenerated polymer, such as from about 55% to about 85%, or about 60% by weight of the regenerated polymer. % To about 85%, or about 65% to about 85%, or about 70% to about 85%, or about 70% to about 80%, or about 75% to about 80% by weight. It is.
In certain embodiments, the weight ratio of the first polyethylene polymer HDPE to the second polyethylene polymer HDPE is from about 0.5: 1 to about 3: 1, for example from about 1: 1 to about 3: 1. Or about 1: 1 to about 2: 1, or about 1: 1 to about 3: 2.

  In certain embodiments, the regenerated polymer is from about 10% to about 75% by weight of the first polyethylene polymer HDPE, eg, from about 20% to about 65% by weight, based on the total weight of the regenerated polymer. Or about 30% to about 65% by weight of the first polyethylene polymer HDPE and about 20% to about 45% of the second polyethylene polymer HDPE. In certain embodiments, the regenerated polymer comprises from about 35% to about 55% by weight of the first polyethylene polymer HDPE and from about 25% to about 40% by weight of the first polymer HDPE. In certain embodiments, the regenerated polymer comprises about 40% to about 50% by weight of a first polyethylene polymer HDPE and about 25% to about 35% by weight of a second polyethylene polymer HDPE. In certain embodiments, the regenerated polymer comprises from about 42% to about 47% first polyethylene polymer HDPE and from about 28 to about 34% by weight second polyethylene polymer HDPE.

In certain embodiments, the relative amount of HDPE is subject to the condition that the total amount of HDPE in the regenerated polymer is from about 50% to about 90% by weight of the regenerated polymer.
The regenerated polymer may include a polymer other than at least two polyethylene polymers. The regenerated polymer may comprise unbound polyethylene polymer.
In certain embodiments, the recycled polymer comprises up to about 20% of polymers other than HDPE, such as LDPE, LLDPE, and polypropylene, any or all of which are polymer waste, such as post-consumption polymer waste. It may be reused from things. In certain embodiments, the regenerated polymer is up to about 20%, such as from about 1% to about 20%, or from about 5% to about 18% by weight, based on the total weight of the regenerated polymer. Or about 10% to about 15%, or about 12% to about 14% by weight polypropylene.

In certain embodiments, the at least one wall of the pipe comprises, for example, up to about 75% by weight unused polymer, up to about 50% by weight unused polymer, or up to about 25% by weight unused polymer. Polymer used, or up to about 15% by weight unused polymer, or up to about 10% by weight unused polymer, or up to about 5% by weight unused polymer, or up to about 1% by weight Of unused polymers. In certain embodiments, at least one wall does not contain unused polymer. In certain embodiments, the pipe contains no unused polymer.
In certain embodiments, playback polymer is from about 0.90 g / cm ³ greater than about 1.15 g / cm ³ or less, for example, greater than about 1.00 g / cm ³ to about 1.10 g / cm ³ or less of the density , for example, greater of about 1.05 g / cm ³ less density than about 1.00 g / cm ³ or from about 1.00 to about density of 1.04 g / cm ^3, or from about 1.00 to about 1.03 g, / with the cm ^3, or from about 1.00 to about 1.02 g / cm ^3, or a density of about 1.01 g / cm ^3. In certain embodiments, the regenerated polymer has a density greater than about 1.00 and not greater than about 1.05 g / cm ³ . The density can be determined according to ISO 1183.

  The functional filler may be present in the regenerated polymer in an amount ranging from about 1% up to about 70% by weight, based on the total weight of the regenerated polymer. For example, this can be from about 2% to about 60%, or from about 3% to about 50%, or from about 4% to about 40%, or about 5%, based on the total weight of the regenerated polymer. % To about 30%, or about 6% to about 25%, or about 7% to about 20%, or about 8% to about 15%, or about 8% to about 12% by weight. It is. The functional filler is about 80% or less of the regenerated polymer, for example, about 70% or less, or about 60% or less, or about 50% or less, based on the total weight of the regenerated polymer, or It may be present in an amount of about 40% or less, or about 30% or less, or about 20% or less, or about 50% or less.

  The functional filler surface treatment (ie, coupling modifier), preferably the compound of formula (1) as described below, is about 0.01 mass based on the total mass of the polymer composition. % To about 4% by weight, for example about 0.02% to about 3.5% by weight, or about 0.05% to about 1.4% by weight, based on the total weight of the regenerated polymer, Or about 0.1% to about 0.7%, or about 0.15% to about 0.7%, or about 0.3% to about 0.7%, or about 0.5% to about 0.7%, or about 0.02% to about 0.5%, or about 0.05% to about 0.5%, or about 0.0%. 1% to about 0.5%, or about 0.15% to about 0.5%, or about 0.2% to about 0.5%, Others in an amount of from about 0.3% to about 0.5% by weight, may be present in the playback polymer.

  Thus, a regenerated polymer that is conveniently bonded in accordance with certain embodiments described herein is at least a virgin polymer, such as virgin polypropylene, in a pipe having a nominal inner diameter of at least about 400 mm. Used to partially replace or even fully replace, pipes having an SN of at least about 4, or at least about 6, or at least about 8 can be obtained (with associated costs and With environmental benefits). Similarly, regenerated polymers that are conveniently bonded in accordance with certain embodiments described herein are unbonded regenerated polymers, such as post-consumer polymer waste, in pipes having a nominal inner diameter of at least about 400 mm. Used to at least partially replace, or even completely replace, unbound regenerated HDPE derived from a blown bottle, such as at least about 4, or at least about 6, or at least Pipes with about 8 SN can be obtained (also with associated costs and environmental benefits). Moreover, the coupling effect allows a smaller amount of polymer (recycled or unused) to be used without adversely affecting the mechanical properties (ie by replacing some with functional fillers). Meaning that in some embodiments, it improves mechanical properties (along with cost benefits).

Functional filler In certain embodiments, the functional filler comprises inorganic particulates and a first compound comprising a terminal propanoic acid group or an ethylene group having one or two adjacent carbonyl groups. Including. The surface treatment agent may be coated on the surface of the inorganic particulate filler. The purpose of the surface treatment agent (eg, coating) is to improve the compatibility of the inorganic particulates and the polymer matrix blended therewith and / or the compatibility of two or more different polymers in the regenerated polymer composition. The cross-linking or grafting of these different polymers is thus improved at one wall of the pipe. In regenerated polymer compositions containing reclaimed and virgin polymers, the functional filler coating can serve to crosslink or graft different polymers.
In other aspects and embodiments of the invention, the coating further or alternatively comprises a compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts, eg, stearic acid or calcium stearate. Including.

Inorganic particulate materials For example, inorganic particulate materials are alkaline earth metal carbonates or sulfates such as calcium carbonate, magnesium carbonate, dolomite, gypsum, hydrous kandite clays such as kaolin, halloysite or ball clay, anhydrous (calcined) It may be a kandite clay such as metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or combinations thereof.
A preferred inorganic particulate material for use in the method according to the first aspect of the invention is calcium carbonate. In the following, the present invention will be discussed primarily in the context of calcium carbonate and in the context of the manner in which the calcium carbonate is processed and / or processed. The present invention should not be construed as limited to such embodiments.

  The granular calcium carbonate used in the present invention can be obtained from natural sources by grinding. Typically, ground calcium carbonate (GCC) is obtained by crushing and then grinding a mineral source such as chalk, marble or limestone, which is a particle size classification to obtain a product with the desired fineness. Can follow the stages. Other techniques such as bleaching, flotation, and magnetic separation can be used to obtain a product with the desired fineness and / or color. The particulate solid material is pulverized spontaneously, i.e. by grinding between the particles of the solid material itself, or the particulate solid material contains particles of a material different from the calcium carbonate to be ground. It is also possible to grind in the presence of a medium. These processes can be performed in the presence or absence of dispersants and biocides that can be added at any stage of the process.

  Precipitated calcium carbonate (PCC) can be used as a source of granular calcium carbonate in the present invention, and can also be produced by any of the known methods available in the art. TAPPI Monograph Series (TAPPI Monograph Series) No. 30, “Paper Coating Pigments”, pp. 34-35 is suitable for use in preparing products for use in the paper industry, but three main commercial methods for producing precipitated calcium carbonate that can also be used in the practice of the present invention. Describes the method. In all three methods, a calcium carbonate feed, such as limestone, is first calcined to quick lime, which is then hydrated in water to calcium hydroxide or lime milk. In the first method, lime milk is directly carbonated with carbon dioxide gas. This process has the advantage of not producing any by-products and is relatively easy to adjust the properties and purity of the calcium carbonate product. In the second process, lime milk is brought into contact with soda ash to produce a calcium carbonate precipitate and a sodium hydroxide solution by metathesis. The sodium hydroxide can be substantially completely separated from calcium carbonate when the process is utilized commercially. In the third major commercial process, lime milk is first contacted with ammonium chloride to obtain a calcium chloride solution and ammonia gas. The calcium chloride solution is then contacted with soda ash to produce precipitated calcium carbonate and sodium chloride solution by metathesis. Crystals can be produced as having a wide variety of different shapes and sizes, depending on the particular reaction process used. The three main forms of PCC crystals are the meteorite, rhombohedron, and rhombohedral shapes, all of which are suitable for use in the present invention, including mixtures thereof.

Wet milling of calcium carbonate involves the formation of an aqueous suspension of calcium carbonate, which may then be milled in the presence of a suitable dispersant. For more information on wet grinding of calcium carbonate, reference may be made, for example, to EP-A-614948, the entire contents of which are incorporated herein by reference. Inorganic particulates such as calcium carbonate may also be prepared by any suitable dry milling technique.
In some situations, addition of other inorganic materials may be included, for example, one or more kaolins, calcined kaolins, wollastonite, bauxite, talc, titanium dioxide or mica may be present.

  If the inorganic particulate material is obtained from a naturally occurring source, some inorganic impurities may contaminate the ground material. For example, naturally occurring calcium carbonate may exist in a state combined with other minerals. Thus, in some embodiments, the inorganic particulate material includes an amount of impurities. In general, however, the inorganic particulate material used in the present invention will contain less than about 5% by weight of other inorganic impurities, preferably less than about 1% by weight.

Unless stated otherwise, the particle size characteristics referred to herein for inorganic particulate materials give (or essentially the same results) well-known conventional methods used in the field of laser light scattering using CILAS 1064 instruments. Measured by other methods). In laser light scattering techniques, the size of particles in powder, suspension and emulsion can be measured using laser beam diffraction based on the application of Mie theory. Such an apparatus has a predetermined e.d., referred to in the art as an "equivalent spherical diameter" (esd). s. This results in a measurement of the cumulative volume percentage of particles having a size smaller than the d value and its plot. This average particle size d ₅₀ is defined as particles having an equivalent particle size smaller than the d ₅₀ value at 50% by volume. s. This is the value of d measured in this way. The term d ₉₀ is the value of the particle size at which 90% by volume of the particles have a particle size less than that value.

The d ₅₀ of the inorganic particulate is less than about 100 μm, such as less than about 80 μm, such as less than about 60 μm, such as less than about 40 μm, such as less than about 20 μm, such as less than about 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as about 6 μm. Less than, for example, less than about 5 μm, such as less than about 4 μm, such as less than about 3 μm, such as less than about 2 μm, such as less than about 1.5 μm, or such as less than about 1 μm. The d ₅₀ of the inorganic particulate may be greater than about 0.5 μm, for example greater than about 0.75 μm, greater than about 1 μm, for example greater than about 1.25 μm, or for example greater than about 1.5 μm. The d ₅₀ of the inorganic particulates is in the range of 0.5-20 μm, such as in the range of about 0.5-10 μm, such as in the range of about 1 to about 5 μm, such as in the range of about 1 to about 3 μm, such as about 1 to about 2 μm. In the range of about 0.5 to about 2 μm, for example in the range of about 0.5 to 1.5 μm, for example in the range of about 0.5 to about 1.4 μm, for example in the range of about 0.5 to about 1.4 μm. A range, such as a range of about 0.5 to about 1.3 μm, such as a range of about 0.5 to about 1.2 μm, such as a range of about 0.5 to about 1.1 μm, such as about 0.5 to about 1. A range of 0 μm, such as a range of about 0.6 to about 1.0 μm, such as a range of about 0.7 to about 1.0 μm, such as a range of about 0.6 to about 0.9 μm, such as about 0.7 to about It may be in the range of 0.9 μm.

The inorganic particulates have a d ₉₀ (also referred to as a top cut) of less than about 150 μm, such as less than about 125 μm, such as less than about 100 μm, such as less than about 75 μm, such as less than about 50 μm, such as less than about 25 μm, such as about 25 μm. It may be less than 20 μm, such as less than about 15 μm, such as less than about 10 μm, such as less than about 8 μm, such as less than about 6 μm, such as less than about 4 μm, such as less than about 3 μm, or such as less than about 2 μm. Advantageously, d ₉₀ may be less than about 25 μm.
The amount of particles smaller than 0.1 μm is typically about 5% or less by volume.

The inorganic particulates can have a particle gradient of about 10 or more. The particle gradient (ie, the gradient of the particle size distribution of the inorganic particulates) is determined by the following formula:
Gradient = 100 × (d ₃₀ / d ₇₀ )
Where d ₃₀ is less than this d ₃₀ value e. s. the particles with d are present in a proportion of 30% by volume e. s. a value of d, also d ₇₀ is smaller e than the d ₇₀ value. s. the particles with d are present in a proportion of 70% by volume. s. The value of d.
The inorganic particulates may have a particle gradient of about 100 or less. The inorganic particulates can have a particle gradient of about 75 or less, or about 50 or less, or about 40 or less, or about 30 or less. The inorganic particulates can have a particle gradient in the range of about 10 to about 50, or in the range of about 10 to about 40.
The inorganic particulates have been treated with a surface treatment agent, i.e., a coupling modifier, whereby the inorganic particulates have a surface treatment on their surface. In certain embodiments, the inorganic particulate is coated with a surface treatment agent.

  At least one wall of the pipe may contain one or more secondary filler components, if desired. The secondary filler component may not be treated with the surface treatment agent. Such additional components, if present, are suitably selected from known filler components for the polymer composition. For example, inorganic particulates used in the functional filler may be used in combination with one or more other known secondary filler components such as titanium dioxide, carbon black and talc. In certain embodiments, the polymer composition includes talc as a secondary filler component. In certain embodiments, the weight ratio of inorganic particulate to secondary filler component is from about 1: 1 to about 10: 1, such as from about 1: 1 to about 5: 1, or from about 2: 1 to about 4. : 1. In certain embodiments, the inorganic particulate of the functional filler is calcium carbonate, such as ground calcium carbonate, and the secondary filler component is uncoated talc. When a secondary filler component is used, this is in an amount of about 0.1% to about 50% by weight of the polymer composition, such as about 1% to about 40%, or about 2% of the regenerated polymer. % To about 30%, or about 2% to about 25%, or about 2% to about 20%, or about 3% to about 15%, or about 4% by weight. It may be present in an amount of up to about 10% by weight.

Surface Treatment Agents Surface treatment agents include compounds containing terminal propanoic acid groups or ethylene groups having one or two adjacent carbonyl groups (also referred to herein as coupling modifiers). The function of the surface treatment agent is to bind the polymer species present in the polymer composition, for example to bind at least two polyethylene polymers. While not wishing to be bound by theory, the coupling may be physical (eg, steric) and / or chemical (eg, covalent or van der Waals bonds) between the polymer and the surface treatment material. (Chemical bond) interaction.

In one embodiment, the surface treatment agent (ie, coupling modifier) has the following formula (1):
A- (X-Y-CO) m (O-B-CO) n OH (1)
Where
A is a moiety containing a terminal ethylenic bond having 1 or 2 adjacent carbonyl groups;
X is O and m is 1-4, or X is N and m is 1.
Y is C _1-18 alkylene or C _2-18 alkenylene;
B is C _2-6 alkylene, n is 0-5,
However, when A contains two carbonyl groups adjacent to the ethylene group, X is N.

In one embodiment, A—X— is a residue of acrylic acid, where (O—B—CO) _n may be a residue of δ-valerolactone or ε-caprolactone or a mixture thereof. , N may be 0.
In another embodiment, AX- is a residue of maleimide, wherein (O—B—CO) _n may be a residue of δ-valerolactone or ε-caprolactone or a mixture thereof, n may be 0.
Specific examples of coupling modifiers are β-carboxyethyl acrylate, β-carboxyhexyl maleimide, 10-carboxydecyl maleimide and 5-carboxypentyl maleimide. Examples of coupling modifiers and methods for their production are described in US-A-7732514, the entire contents of which are hereby incorporated by reference.

In another embodiment, the coupling modifier is β-acryloyloxypropanoic acid or an oligomeric acrylic acid represented by the following formula (2):
_{CH 2 = CH-COO [CH} 2 -CH 2 -COO] n H (2)
In formula, n represents the number of the range of 1-6.
In one embodiment, n is 1, or 2, or 3, or 4, or 5, or 6.
The oligomeric acrylic acid of formula (2) is a temperature in the range of about 50 ° C. to 200 ° C. in the presence of 0.001 to 1% by weight of a polymerization inhibitor, which may be under high pressure and in the presence of an inert solvent. Up to, it can be produced by heating acrylic acid. Examples of coupling modifiers and methods for their production are described in US-A-4267365, the entire contents of which are hereby incorporated by reference.

In another embodiment, the coupling modifier is β-acryloyloxypropanoic acid. This species and its method of manufacture are described in US-A-3888912, the entire contents of which are incorporated herein by reference.
The surface treatment agent is present in the functional filler in an amount effective to achieve the desired result. This amount will vary from one coupling modifier to another and may depend on the exact composition of the inorganic particulates. For example, the coupling modifier may be present in an amount of about 5% or less, such as about 2% or less, or such as about 1.5% or less, based on the total weight of the functional filler. In one embodiment, the coupling modifier is about 1.2% or less, such as about 1.1% or less, such as about 1.0% or less, such as about 1.0%, based on the total weight of the functional filler. 0.9% by weight or less, for example about 0.8% by weight or less, for example about 0.7% by weight or less, for example about 0.6% by weight or less, for example about 0.5% by weight or less, for example about 0.4% by weight. Below, for example in an amount of about 0.3% by weight or less, for example about 0.2% by weight or less, or for example about 0.1% by weight or less, in the functional filler. Typically, the coupling modifier is present in the functional filler in an amount greater than about 0.05% by weight. In further embodiments, the coupling modifier is in the range of about 0.1 to 2 wt%, such as in the range of about 0.2 to about 1.8 wt%, or about 0.3 to about 1.6 wt%. Or about 0.4 to about 1.4% by weight, or about 0.5 to about 1.3% by weight, or about 0.6 to about 1.2% by weight, or about In the functional filler in an amount in the range of 0.7 to about 1.2 wt%, or in the range of about 0.8 to about 1.2 wt%, or in the range of about 0.8 to about 1.1 wt%. Exists.

In certain embodiments, the terminal propanoic acid group or ethylene group compound / compound (s) having one or two adjacent carbonyl groups is the single species present in the surface treatment agent.
In certain embodiments, the surface treatment agent further comprises a second compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts and combinations thereof.

In one embodiment, the one or more fatty acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidin. Selected from the group consisting of acid, vaccenic acid, linoleic acid, linoelaidic acid, α-linoleic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid and combinations thereof. In another embodiment, the one or more fatty acids are saturated fatty acids or unsaturated fatty acids. In another embodiment, the fatty acids are C ₁₂ -C ₂₄ fatty acids, such as C ₁₆ -C ₂₂ fatty acids, which may be saturated or unsaturated. In one embodiment, the one or more fatty acids is stearic acid and may be combined with other fatty acids.
In another embodiment, the salt of one or more fatty acids is a metal salt of the aforementioned fatty acids. The metal may be an alkali metal or alkaline earth metal or zinc. In one embodiment, the second compound is calcium stearate.

  When present, the second compound is present in the functional filler in an amount effective to achieve the desired result. This amount will vary from one coupling modifier to another and may depend on the exact composition of the inorganic particulates. For example, the second compound may be present in an amount of about 5% or less, such as about 2% or less, or such as about 1% or less, based on the total weight of the functional filler. In one embodiment, the second compound is about 0.9% or less, such as about 0.8% or less, such as about 0.7% or less, such as about 0, based on the total weight of the functional filler. .6% or less, such as about 0.5% or less, such as about 0.4% or less, such as about 0.3% or less, such as about 0.2% or less, or such as about 0.1%. It is present in the functional filler in the following amounts. Typically, the second compound, when present, is present in the functional filler in an amount greater than about 0.05% by weight. The mass ratio of the coupling modifier to the second compound ranges from about 5: 1 to about 1: 5, such as from about 4: 1 to about 1: 4, such as from about 3: 1 to about 1: 3. In the range of about 2: 1 to about 1: 2, or for example about 1: 1. The amount of coating comprising the first compound (i.e., coupling modifier) and the second compound (i.e., one or more fatty acids or salts thereof) is such that a single layer deposition amount is provided on the surface of the inorganic particulates. Is the amount calculated. In embodiments, the weight ratio of the first compound to the second compound ranges from about 4: 1 to about 1: 3, such as from about 4: 1 to about 1: 2, such as from about 4: 1 to about 1. A range of 1: 1, such as a range of about 4: 1 to about 2: 1, such as a range of about 3.5: 1 to about 1: 1, such as a range of about 3.5: 1 to 2: 1, or For example, in the range of about 3.5: 1 to about 2.5: 1.

In certain embodiments, the surface treatment agent does not include a compound selected from the group consisting of one or more fatty acids and one or more fatty acid salts.
The regenerated polymer may further contain a peroxide-containing additive. In one embodiment, the peroxide-containing additive comprises dicumyl peroxide or 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane. The peroxide-containing additive need not necessarily be included in the surface treatment agent, but can instead be added during the blending operation of the functional filler and regenerated polymer, as will be described below. For example, in some polymer systems such as HDPE, inclusion of peroxide-containing additives can facilitate cross-linking of polymer chains. In other polymer systems such as polypropylene, breakage of the polymer chain can be promoted by including a peroxide-containing additive. The peroxide-containing additive can be present in an amount effective to achieve the desired result. This amount is different for each coupling modifier and may depend on the exact composition of the inorganic particulates and polymer. For example, the peroxide-containing additive is about 1% or less, such as about 0.5% or less, such as about 0.1%, such as about 0.1%, based on the weight of the regenerated polymer to which the peroxide-containing additive is to be added. It may be present in an amount of 0.09% or less, such as about 0.08% or less, or such as about 0.06% or less. Typically, the peroxide-containing additive, if present, is present in an amount greater than about 0.01% by weight, based on the weight of the regenerated polymer.

  The functional filler is a mixture of inorganic particulates, surface treatment agent and optional peroxide-containing additives, using conventional methods, for example using steel and Kaurishaw high strength mixers, preferably at a temperature below 80 ° C. It can manufacture by mixing with. The surface treating agent compound (s) can be applied after the inorganic particulates have been crushed but before the inorganic particulates are added to any regenerated polymer composition. For example, the surface treatment agent can be added to the inorganic particles in the stage of mechanically deaggregating the inorganic particles. The surface treatment agent can be applied during deagglomeration performed in a milling machine.

Optional additional filler components The functional filler may further comprise an antioxidant. Suitable antioxidants include, but are not limited to, organic molecules consisting of hindered phenols and amine derivatives, organic molecules consisting of phosphates and low molecular weight hindered phenols, and thioesters. Exemplary antioxidants include Irganox 1010 and Irganox 215, and blends of Irganox 1010 and Irganox 215. The amount of antioxidant may range from about 0.01% to about 5% by weight based on the content of regenerated polymer, for example, about 0.05% by weight based on the content of regenerated polymer. % To about 2.5%, or about 0.05% to about 1.5%, or about 0.05% to about 1.0%, or about 0.05% to about 0.0%. It may be 5 wt%, or about 0.05 wt% to about 0.25 wt%, or about 0.05 wt% to about 0.15 wt%.

Pipe Manufacturing Method In certain embodiments, at least one wall is formed, eg, extruded, from a polymer resin composition that includes, for example, a suitable amount of regenerated polymer, and may include a functional filler and an impact modifier. Molded.
The compounding operation itself is a technique well known to those skilled in the art of polymer processing and manufacturing. It is understood in the art that compounding operations are distinct from blending or mixing steps that are performed at a temperature lower than the temperature at which the components become melted.

  Such methods include compounding and extrusion processes. The compounding process can be carried out using a twin screw compounder, for example, a Baker Perkins 25 mm twin screw compounder. Polymers, functional fillers, optional impact modifiers and optional peroxide-containing additives and / or optional antioxidants can be premixed and fed from a single hopper. The resulting melt can be cooled, for example, in a water bath and then pelletized.

  The formulated composition may further comprise additional components such as slip aids (eg, Erucamide), processing aids (eg, Polybatch® AMF-705), mold release agents and antioxidants. An agent can be included. Suitable mold release agents will be readily apparent to those skilled in the art and include fatty acids and the zinc, calcium, magnesium and lithium salts of fatty acids and organophosphates. Specific examples thereof are stearic acid, zinc stearate, calcium stearate, magnesium stearate, lithium stearate, calcium oleate and zinc palmitate. Slip and processing aids, and mold release agents are added in amounts less than about 5% by weight, based on the weight of the masterbatch. The pipe can then be subjected to extrusion, compression molding or injection molding utilizing conventional techniques known in the art, as will be readily apparent to those skilled in the art.

  In certain embodiments, the at least two polyethylene polymers are each contained in separate polymer streams and fed separately to the blender. For example, a first polyethylene containing HDPE is fed to the blender as a first polymer stream, a second polyethylene polymer is fed to the blender as a second polymer stream, and the functional filler is a third polymer stream. A stream is fed to the blender and any impact modifier is fed to the blender as a fourth stream. In such embodiments, the second polymer stream comprising the second polyethylene polymer may be part of a polymer stream comprising other polymer components such as polypropylene, LDPE, and / or LLDPE. In other embodiments, any other polymer component may be fed to the blender via a separate feed stream.

In certain embodiments, the at least two polyethylene polymers are part of the same polymer stream. Thus, in such an embodiment, a single feed stream that may include at least two polyethylene polymers and other polymer components such as polypropylene, LDPE, and / or LLDPE is fed to the blender.
In certain embodiments, the functional filler is not contacted with the polymer prior to blending with the at least two polyethylene polymers.
The relative amount of each component will be that amount capable of making the regenerated polymer according to the invention and thus the pipe.

Example 1 Preparation of Specimens Three polymer compositions were prepared as follows.
Comparative composition A
Using a Baker Perkins 25 mm twin screw compounder, ground calcium carbonate (d ₅₀ = 0.8 μm) coated with a coupling modifier according to formula (1) and recycled mixed polyolefin feed containing HDPE and PP. Prepared. The recycled mixed polyolefin feedstock was derived from an injection molding material.
The mixed polyolefin feed had an MFR at 190 ° C./2.16 kg of 1.5.
The amount of surface treatment applied to the calcium carbonate was calculated to obtain a monolayer coating on the surface.
The resulting polymer composition contained 20% by weight surface treated calcium carbonate, 56% HDPE and 24% polypropylene.
Comparative composition B
Pre-formed composition A (50% by weight) was compounded with a different polyethylene polymer (50% by weight) derived from recycled blow molded bottles according to the procedure described for comparative composition A.
The second polyethylene polymer had an MFR of 190 ° C / 2.16 kg of 0.4.
The resulting polymer composition comprises 10% by weight surface treated calcium carbonate, 31.5% by weight HDPE from mixed polyolefin feedstock, and 45% HDPE from polyethylene from recycled blow molded bottles, and 13. 5% polypropylene was included. Both polyethylene polymers are not bonded.

-Composition 1 (of the invention)
The same surface-treated calcium carbonate and mixed polyolefin feed as used to prepare Comparative Composition A and the polyethylene polymer derived from the regenerated blow molded bottle and regenerated as described above. And blended. The relative amount of each component is 10% by weight surface treated calcium carbonate, 31.5% by weight HDPE from mixed polyolefin feedstock, 13.5% by weight polypropylene, and blow molding. Selected to contain 45 wt% HDPE from polyethylene from bottle. Both polyethylene polymers are bonded.

Example 2 Mechanical Testing Test specimens of Compositions A, B, and 1 were prepared.
After adjusting the specimen at 23 ° C., the sample was tested as follows.
The resilience (toughness) at −20 ° C. of each specimen was tested according to ISO179.
The rigidity (flexural modulus) of each specimen was tested according to ISO178.
The elongation at break of each specimen was tested according to ISO 527.
These results are summarized in FIGS.

Example 3
-Preparation of compounded regenerated polymer resin A Recycled mixed polyolefin feed (1.5 of 190) comprising ground calcium carbonate (d ₅₀ = 0.8 μm) coated with a coupling modifier according to formula (1) and HDPE and PP With an MFR of 0 ° C./2.16 kg) using a Baker Perkins 25 mm twin screw compounder.
The amount of surface treatment applied to the calcium carbonate was calculated to obtain a monolayer coating on the surface.
-Preparation of compounded recycled polymer resin B Same surface treated calcium carbonate and mixed polyolefin feed as used to prepare resin A and polyethylene polymer derived from recycled bottle (190 ° C / 2.16 kg of 0.4 Were fed to the same Baker Perkins 25mm twin screw compounder and prepared using this. Both polyethylene polymers are bonded.

Example 4
Test piece preparation Regenerated polymer blends based on weight percentage are listed in Table 1. All blends were prepared via melt mixing with a Coperion ZSK18 twin screw extruder in the presence of 0.1 wt% antioxidant (based on polymer content). The impact modifier, when present, was an ethylene-octene copolymer having an MFR of about 1 at 190 ° C./2.16 kg. The barrel temperature was maintained at 200, 205, 210, 220, 230, and 240 ° C. from the hopper to the die. The screw speed was set to 600 rpm and the feed speed was set to 6.0 kg / hour. The hot extrudate was immediately quenched in water and pelletized. A test piece for mechanical testing was then generated.

-Mechanical test of test pieces The impact strength (unnotched Charpy impact strength at -20 ° C) of each test piece was tested according to ISO 179 using an Instron Ceast drop impact tester. These results correspond to the average of complete fracture measurements for each specimen.

  The elongation at break of each specimen was tested according to ISO 527 using a Tinius Olsen bench top tensile tester, and these results correspond to the average of eight measurements for each specimen.

The results are summarized in Table 1 below.

Claims (43)

A polymer composition comprising:
A functional filler comprising at least two polyethylene polymers, and inorganic particles, and a surface treatment agent on the surface of the inorganic particles;
The at least two polyethylene polymers are combined;
The polymer composition, wherein the first of the at least two polyethylene polymers comprises HDPE.   The polymer composition of claim 1, wherein the polyethylene polymer is a recycled polymer, such as a polymer waste after recycled consumption. 3. (i) Resilience at -20 <0> C greater than 60 kJ / m < ² > and / or (ii) Elongation at break greater than 32% and / or (iii) Flexural modulus greater than 800 MPa. Polymer composition.   The second of the at least two polyethylene polymers comprises HDPE, and the HDPE of the second polyethylene polymer is different from the HDPE of the first polyethylene polymer. A polymer composition according to 1.   The first of the at least two polyethylene polymers has an MFR at 190 ° C./2.16 kg of less than 0.75 g / 10 minutes, and the second of the at least two polyethylene polymers is The polymer composition according to claim 1, which may have an MFR at 190 ° C./2.16 kg of 0.75 g / 10 min or more.   The polymer composition according to claim 1, further comprising polypropylene, wherein the polypropylene may be recycled polypropylene.   The inorganic particulates are alkaline earth metal carbonates or sulfates such as calcium carbonate, magnesium carbonate, dolomite, gypsum, hydrous kandite clay such as kaolin, halloysite or ball clay, anhydrous (calcined) kandite clay such as Metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or combinations thereof, wherein the inorganic particulates are calcium carbonate, such as ground calcium carbonate, The polymer composition may further include a second filler that has not been treated with a surface treatment agent, and the second filler may be talc. The polymer composition according to any one of the above. The surface treatment agent includes a first compound having a terminal propanoic acid group or an ethylene group having one or two adjacent carbonyl groups, and the first compound has the formula (1):
A- (X-Y-CO) m (O-B-CO) n OH (1)
You may have
Where
A is a moiety containing a terminal ethylenic bond having 1 or 2 adjacent carbonyl groups;
X is O and m is 1-4, or X is N and m is 1;
Y is C _1-18 alkylene or C _2-18 alkenylene;
B is C _2-6 alkylene; n is 0-5;
Provided that when A contains two carbonyl groups adjacent to the ethylene group, X is N.
The polymer composition according to any one of claims 1 to 7.   9. The polymer composition according to any one of claims 1 to 8, wherein the functional filler is present in an amount ranging from about 5 to about 25% by weight of the polymer composition.   10. The polymer composition according to any one of claims 1 to 9, wherein the HDPE of the first polyethylene polymer is present in an amount ranging from about 10 to about 75% by weight of the polymer composition.   A method of reducing blending of polymer components during manufacture of a product, comprising (i) at least two types of HDPE and a functional filler comprising inorganic particulates having a surface treating agent on the surface. And (ii) forming a product therefrom.   A product formed from the polymer composition according to any one of claims 1 to 10, for example a pipe.   Use of the polymer composition according to any one of claims 1 to 10 for improving the mechanical properties of a product formed from the composition.   The method for producing a polymer composition according to claim 1, comprising mixing the at least two polyethylene polymers with the functional filler.   15. The method of claim 14, wherein (i) the at least two polyethylene polymers are each included in a separate polymer stream, or (ii) the at least two polyethylene polymers are part of the same polymer stream. Method.   A pipe having at least one wall, the pipe having a nominal inner diameter of at least about 400 mm and an SN of at least about 4, wherein the at least one wall is based on the total mass of the at least one wall; And said pipe comprising at least about 25% by weight recycled polymer.   The pipe of claim 16, wherein the nominal inner diameter is at least about 500 mm, such as at least about 600 mm.   18. A pipe according to claim 16 or 17, having an SN of at least about 6, for example at least about 8.   17. Pipe according to claim 16, fulfilling the requirements of the standard BS EN 13476-3: 2007 + A1: 2009 as long as the standard relates to unpressurized underground drainage and sewage pipes.   20. Pipe according to any one of claims 16 to 19, which is a single wall or double wall pipe.   The pipe according to any one of claims 16 to 20, which is a corrugated pipe.   The pipe according to any one of claims 16 to 21, wherein the pipe is a double-walled pipe, for example a corrugated double-walled pipe, and the at least wall is the outer wall of the pipe.   23. A pipe according to any one of claims 16 to 22, wherein the at least one wall comprises at least about 50 wt% regenerated polymer, for example at least about 70 wt% regenerated polymer.   24. A pipe according to any one of claims 16 to 23, wherein the at least one wall comprises up to about 75 wt% regenerated polymer, for example up to about 85 wt% regenerated polymer.   The recycled polymer is a mixture of different polymer species, such as a mixture of polyethylene (PE) and polypropylene (PP), such as a mixture of HDPE and PP, or a mixture of HDPE, PP and low density polyethylene (LDPE), or at least 25. A mixture of two different types of HDPE and PP, for example HDPE from blow molded bottles, HDPE from sources other than blow molded bottles, and PP. The pipe according to any one of the above.   The regenerated polymer comprises a mixture of at least two polyethylene polymers that may be bound to the inorganic particulate material via a surface treatment on the surface of the inorganic particulate (also referred to as functional filler); The first of the at least two polyethylene polymers includes HDPE or is HDPE, and the second of the at least two polyethylene polymers may be HDPE or may include HDPE 26. The pipe of claim 25, wherein the HDPE of the second polyethylene polymer is different from the HDPE of the first polyethylene polymer.   The first of the at least two polyethylene polymers has an MFR of less than 0.75 g / 10 minutes (2.16 kg at 190 ° C.) and the second of the at least two polyethylene polymers 27. The pipe according to claim 26, which may have an MFR of 0.75 g / 10 min or more (2.16 kg at 190 ° C.).   28. A pipe according to claim 26 or 27, further comprising recycled polypropylene.   The at least one wall may include a functional filler including inorganic particulates, and may include a surface treatment agent on the surface of the inorganic particulates, whereby the regenerated polymer is inorganic through the surface treatment agent. 29. Pipe according to any one of claims 16 to 28, which is bonded to a particulate material.   The inorganic particulates are alkaline earth metal carbonates or sulfates such as calcium carbonate, magnesium carbonate, dolomite, gypsum, hydrous kandite clay such as kaolin, halloysite or ball clay, anhydrous (calcined) kandite clay such as Metakaolin or fully calcined kaolin, talc, mica, perlite or diatomaceous earth, or magnesium hydroxide, or aluminum trihydrate, or combinations thereof, wherein the inorganic particulates are calcium carbonate, such as ground calcium carbonate, 30. Any of the claims 26-29, wherein the pipe may further comprise a second filler not treated with a surface treatment agent, and the second filler may be talc. The pipe according to claim 1. The surface treatment agent includes a first compound having a terminal propanoic acid group or an ethylene group having one or two adjacent carbonyl groups, and the first compound has the formula (1):
A- (X-Y-CO) m (O-B-CO) n OH (1)
You may have
Where
A is a moiety containing a terminal ethylenic bond having 1 or 2 adjacent carbonyl groups;
X is O and m is 1-4, or X is N and m is 1;
Y is C _1-18 alkylene or C _2-18 alkenylene;
B is C _2-6 alkylene; n is 0-5;
Provided that when A contains two carbonyl groups adjacent to the ethylene group, X is N.
The pipe according to any one of claims 26 to 30.   32. The functional filler is present in an amount ranging from about 5% to about 25%, such as from about 5% to about 15% by weight, based on the total weight of the regenerated polymer. The pipe according to any one of the above.   33. A pipe according to any one of claims 16 to 32, wherein the HDPE of the first polyethylene polymer is present in an amount ranging from about 10 to about 75% by weight of the regenerated polymer.   34. A pipe according to any one of claims 16 to 33, wherein the at least one wall comprises an impact modifier, for example an impact modifier up to about 10% by weight.   35. A pipe according to claim 34, wherein the impact modifier is an elastomer, for example a polyolefin elastomer.   36. Pipe according to claim 35, wherein the polyolefin elastomer is a copolymer of ethylene and another olefin, for example octane, and / or butene and / or styrene, for example a copolymer of ethylene and octene. .   The pipe of claim 34, wherein the impact modifier is a copolymer of styrene and butadiene. The polyolefin elastomer has a density of about 0.80 to about 0.95 g / cm ³ and / or 0.2 g / 10 min (2.16 kg at 190 ° C.) to about 30 g / 10 min (2 at 190 ° C. 36.), for example, from about 0.5 g / 10 min (2.16 kg at 190 ° C.) to about 1.5 g / 10 min (2.16 kg at 190 ° C.). The listed pipe.   A compounded polymer resin containing an appropriate amount of a regenerated polymer and a functional filler, which may contain an impact modifier, wherein the functional filler comprises inorganic particulates and a surface treatment agent on the surface of the functional filler. 39. Pipe according to any one of claims 16 to 38, wherein the at least one wall is formed, e.g. extruded, from a compounded polymer resin comprising   40. Pipe according to claim 39, wherein the amount and / or composition of regenerated polymer is selected to produce the pipe according to any one of claims 16-40.   Combined and at least partially, optionally entirely, to replace unused polymer, such as unused polypropylene, in a pipe having a nominal inner diameter of at least about 400 mm and an SN of at least about 4. Use of a regenerated polymer as defined in any one of 16-40.   In pipes having a nominal inner diameter of at least about 400 mm and an SN of at least about 4, unbound reclaimed polymer, for example unconsumed reclaimed HDPE polymer from post-consumer polymer waste, eg blow molded bottles, is at least partially 41. Use of a regenerated polymer as defined in any one of claims 16 to 40, optionally and entirely for replacement.   In pipes having a nominal inner diameter of at least about 400 mm and an SN of at least about 4, unbound recycled polymer and virgin polypropylene, such as unbound recycled HDPE polymer derived from post-consumer polymer waste such as blow molded bottles 41. Use of a regenerated polymer as combined and as defined in any one of claims 16 to 40 to replace at least partially, optionally entirely.

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